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Application of Lithium/Halide Exchange Reactions to the Synthesis of Complex Polymer Architectures

Permanent Link: http://ufdc.ufl.edu/UFE0017512/00001

Material Information

Title: Application of Lithium/Halide Exchange Reactions to the Synthesis of Complex Polymer Architectures Investigation of Their Self-Assembling Properties at the Air/Water Interface
Physical Description: 1 online resource (281 p.)
Language: english
Creator: Matmour, Rachid
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: amphiphilic, anionic, architectures, carbanions, copolymerization, crosslinking, dendrimers, interface, living, metalation, nanomaterials, polybutadiene, polyethyleneoxide, polystyrene, stars
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: An entire set of hydrocarbon-soluble polycarbanionic initiators and macroinitiators was synthesized by using a simple halogen-lithium exchange reaction (Gilman?s reaction) carried out on multibromo molecule and macromolecule precursors. Using these multicarbanionic (macro)initiators an entire set of complex polymer architectures has been synthesized by anionic polymerization using a divergent method. This strategy was first applied to the preparation of simple polymer architectures such as poly(styrene-b-butadiene-b-styrene) triblock copolymers with excellent mechanical properties, obtained using a new hydrocarbon soluble dicarbanionic organolithium initiator containing a side C15-alkyl chain. The same exchange reaction has been successfully applied to generate tri- and tetracarbanionic species from tris- and tetrakis-bromoaryl compounds. The use of a ?/? ligand was instrumental in obtaining polycarbanionic initiators soluble in apolar medium, and the subsequent preparation of various well-defined three and four-armed polystyrene and polybutadiene stars synthesized by the ?core-first? method. The efficiency of the latter was even exploited to synthesize poly(butadiene-b-ethylene oxide) (PB-b-PEO)n amphiphilic star block copolymers and poly(styrene-b-butadiene-b-methyl methacrylate) (P(S-b-B-b-M)n) star block terpolymers (n = 3 or 4). The potential of PB-b-PEO star block copolymer to self-assemble at the air/water interface was exploited to synthesize a two-dimensional polymeric nanomaterial consisting of a continuously cross-linked polybutadiene two-dimensional network with poly(ethylene oxide) domains of controlled sizes trapped within the network. To reach that goal, novel (PB(Si(OEt)3)-b-PEO)3 star block copolymers were designed by hydrosilylation of the pendant double bonds of (PB-b-PEO)3 star block copolymer precursors with triethoxysilane. Self-condensation of the triethoxysilane groups under acidic conditions led to a successful cross-linking of the polybutadiene blocks directly at the air/water interface without any additives or reagents. Finally, the Gilman reaction was extended on omega,omega?-dibromo chain-end polymers after the introduction of a branching agent whose halogen atoms are carried by separate aryl rings to afford hydrocarbon-soluble polycarbanionic macroinitiators. This provided an efficient synthetic route to the asymmetric and ?miktoarm? star (co)polymers based on the combination of different polymers such as polystyrene, polybutadiene, and polyisoprene. By the reiteration of this sequence of reactions (branching and halogen-lithium exchange reactions) starting from a tetrafunctional initiator, dendrimer-like PS and PB up to the seventh and third generations, respectively, could be successfully synthesized.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Rachid Matmour.
Thesis: Thesis (Ph.D.)--University of Florida, 2007.
Local: Adviser: Duran, Randolph.
Local: Co-adviser: Enholm, Eric J.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0017512:00001

Permanent Link: http://ufdc.ufl.edu/UFE0017512/00001

Material Information

Title: Application of Lithium/Halide Exchange Reactions to the Synthesis of Complex Polymer Architectures Investigation of Their Self-Assembling Properties at the Air/Water Interface
Physical Description: 1 online resource (281 p.)
Language: english
Creator: Matmour, Rachid
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: amphiphilic, anionic, architectures, carbanions, copolymerization, crosslinking, dendrimers, interface, living, metalation, nanomaterials, polybutadiene, polyethyleneoxide, polystyrene, stars
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: An entire set of hydrocarbon-soluble polycarbanionic initiators and macroinitiators was synthesized by using a simple halogen-lithium exchange reaction (Gilman?s reaction) carried out on multibromo molecule and macromolecule precursors. Using these multicarbanionic (macro)initiators an entire set of complex polymer architectures has been synthesized by anionic polymerization using a divergent method. This strategy was first applied to the preparation of simple polymer architectures such as poly(styrene-b-butadiene-b-styrene) triblock copolymers with excellent mechanical properties, obtained using a new hydrocarbon soluble dicarbanionic organolithium initiator containing a side C15-alkyl chain. The same exchange reaction has been successfully applied to generate tri- and tetracarbanionic species from tris- and tetrakis-bromoaryl compounds. The use of a ?/? ligand was instrumental in obtaining polycarbanionic initiators soluble in apolar medium, and the subsequent preparation of various well-defined three and four-armed polystyrene and polybutadiene stars synthesized by the ?core-first? method. The efficiency of the latter was even exploited to synthesize poly(butadiene-b-ethylene oxide) (PB-b-PEO)n amphiphilic star block copolymers and poly(styrene-b-butadiene-b-methyl methacrylate) (P(S-b-B-b-M)n) star block terpolymers (n = 3 or 4). The potential of PB-b-PEO star block copolymer to self-assemble at the air/water interface was exploited to synthesize a two-dimensional polymeric nanomaterial consisting of a continuously cross-linked polybutadiene two-dimensional network with poly(ethylene oxide) domains of controlled sizes trapped within the network. To reach that goal, novel (PB(Si(OEt)3)-b-PEO)3 star block copolymers were designed by hydrosilylation of the pendant double bonds of (PB-b-PEO)3 star block copolymer precursors with triethoxysilane. Self-condensation of the triethoxysilane groups under acidic conditions led to a successful cross-linking of the polybutadiene blocks directly at the air/water interface without any additives or reagents. Finally, the Gilman reaction was extended on omega,omega?-dibromo chain-end polymers after the introduction of a branching agent whose halogen atoms are carried by separate aryl rings to afford hydrocarbon-soluble polycarbanionic macroinitiators. This provided an efficient synthetic route to the asymmetric and ?miktoarm? star (co)polymers based on the combination of different polymers such as polystyrene, polybutadiene, and polyisoprene. By the reiteration of this sequence of reactions (branching and halogen-lithium exchange reactions) starting from a tetrafunctional initiator, dendrimer-like PS and PB up to the seventh and third generations, respectively, could be successfully synthesized.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Rachid Matmour.
Thesis: Thesis (Ph.D.)--University of Florida, 2007.
Local: Adviser: Duran, Randolph.
Local: Co-adviser: Enholm, Eric J.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0017512:00001


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APPLICATION OF LITHIUM/HALIDE EXCHANGE REACTIONS TO THE SYNTHESIS
OF COMPLEX POLYMER ARCHITECTURES: INVESTIGATION OF THEIR SELF-
ASSEMBLING PROPERTIES AT THE AIR/WATER INTERFACE



















By

RACHID MATMOUR


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA AND THE UNIVERSITY OF BORDEAUX I IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA
UNIVERSITY OF BORDEAUX 1

2007





























Copyright 2007 Rachid Matmour



































To my parents and my brother--thanks for everything.









ACKNOWLEDGMENTS

This dissertation is the result of 4 years of research between the Laboratoire de Chimie

des Polymeres Organiques (LCPO) at the University of Bordeaux 1 and the Center for

Macromolecular Science and Engineering (Department of Chemistry) at the University of

Florida.

Graduate school is one of the most difficult times in a person's life. During the time that I

was engaged in this study, the life was some days nice because of the interesting experimental

results obtained after many hours, days, and months of work which made me proud, and more

difficult some other days because of the experiments that I had to repeat week after week until I

fixed what was wrong. After these four years of research, I can say for sure that graduate school

teaches patience and perseverance.

However, without the support of others I could not have achieved this seemingly

insurmountable goal. First and foremost I would like to thank my parents, Houcine and Fettouma

Matmour. They arrived in France in the 1970s from Morocco. Even if they are not really rich,

they gave me something that one cannot buy: their love and guidance throughout my life. Their

unwavering confidence has enabled me to continue when my efforts have fallen short, never

doubting that the next try will be a successful one. Their unconditional love is something that I

have relied on regardless of the time period or distance between us. I am proud to be their son,

and I am proud to say that this is the foundation on which all else has been possible. I do not

hesitate to say that I could not have completed graduate school without them. Because of all

these reasons, this dissertation is dedicated to my parents.

With no less sincerity, I would also like to thank especially five persons for the impact each

one has made on me as a scientist throughout my undergraduate and graduate school. First, I am

extremely grateful for the assistance and advice I received from Prof. Yves Gnanou. Since the









time I started my Ph.D. in 2002 under his supervision, I learned a lot from his experience. I

greatly appreciate the time he has taken to enlighten me with his perspectives on science,

writing, and the world of chemistry as it stands today. His experienced advice has been an

integral part of my education and has given me a deeper understanding of what is needed to be

successful as a research chemist. I also am grateful for the incredible effort he has put forth to

strengthen my research, and especially this document. Finally, I would like to thank him for the

good advice he gave me concerning my future after the Ph.D.

I would like to thank Prof. Randolph Duran, who was my advisor at the University of

Florida. First, without his help I would never have had the chance to spend two years at the

University of Florida for this j oint Ph.D. program. This gave me the opportunity to be a Research

Assistant in Prof. Duran's group working on Langmuir and Langmuir-Blodgett films and a

Teaching Assistant for Prof. Horvath for one year. I thank the students whom I was privileged to

teach and from whom I also learned much, especially Stacey Gray (I will miss her!), Kathleen

Evans, Natalie Nix, Alicia Kinsey, Ashley Holmes, Wilfredo Herrera, John Keenan, Ashley

Dekleine, Leigh Klein, Lauren Kelley, Tommasina Miller, and Erin McGuinn (I thank them for

making Gainesville like my home!). Because of all these good experiences I had at the

University of Florida, I am extremely grateful to Prof. Randolph Duran.

I would like to thank Dr. Daniel Taton, Assistant-Professor at the LCPO, whom I met in

2001. He was my advisor during my pre-Ph.D. year. During this time he first showed me the

importance for a researcher to deeply study the literature before starting any experiments at the

bench. I appreciated his really good experience in the area of macromolecular complex

architectures and radical controlled polymerization. Because of him, I really understood the









interest of synthesizing different kinds of polymeric architectures and studying their properties

and applications. My interest in this science comes from there!

I owe a special note of gratitude to Dr. Eric Cloutet, CNRS Scientist at the LCPO, who first

introduced me to the polymer sciences. I met him in March 2001 and worked on my

undergraduate research under his supervision. During this period, he first showed me how to

correctly and safely manipulate the experiments, but he was also the first one to show me the

interests and applications of polymer chemistry. Because of him, I decided to focus on polymer

chemistry and to study more deeply this science.

Finally, I wish to thank my friend, Thomas Joncheray, for his collaboration on different

projects. I met Emilie Galand (his girlfriend) and him for the first time in 2003 at the University

of Florida. They helped me a lot concerning all the administrative affairs at the University of

Florida (I thank Emilie, who is really the best!). Besides that, I had the chance to work with

Thomas on the synthesis of two-dimensional polymeric nanomaterials, which gave two

publications (that was a really good team!). Even if we were working very hard during the day,

that was always with a good mood in the lab, which helps working very late in the night.

Because of the different events we shared in the lab, I think we will remember our stay in Prof.

Duran's group for the rest of our life.

Many people on the faculty and staff of the Graduate School of the University of Florida,

the Center for Macromolecular Science and Engineering, and the LCPO assisted me in various

ways during my course of studies. I am especially grateful to Dr. Ben Smith, Lori Clark,

Catherine Roulinat, Corinne Gongalves de Carvalho, Nicole Buzat, Bernadette Guillabert, and

Emmanuel Ibarboure.









I extend many thanks to my colleagues and friends: David Lanson (the "Globtrotter"), the

French Running Team of LCPO (Profs. Henri Cramail and Sebastien Lecommandoux, Dr.

Daniel Taton, Dr. Eric Cloutet, Romain Perrier-Cornet, Nicolas Guidolin), Amelie Baron (the

most kindly girl), the basketball team of Gainesville (Thomas Joncheray, Pierre Beaujuge,

Benoit Lauly, James Leonard, Christophe Grenier, Dimitri Hirsch-Weil), Thomas Dalet (alias the

"Joker"!i), Jan Merna (alias "Crazy Man"), Renjith Devasia, the N1-33 team ("Colonel" Cloutet,

Anne de Cuendias, Cecile Bouilhac, Pierre Chambon).

I would also like to thank all the people I have had the pleasure to meet during my stay at

the Laboratoire de Chimie des Polymeres Organiques (University of Bordeaux 1) and at the

Center for Macromolecular Science and Engineering (Department of Chemistry, University of

Florida).

Finally, the members of my dissertation committee, Lisa McElwee-White, Monique

Mauzac, Eric Enholm, Ben Dunn, Georges Hadziioannou, Daniel Taton, Randolph S. Duran and

Yves Gnanou, have generously given their time and expertise to better my work. I would like to

thank them for their judgment and their contribution to this work.











TABLE OF CONTENTS


page

ACKNOWLEDGMENTS .............. ...............4.....


LIST OF TABLES ................ ...............12........... ....

LIST OF FIGURES .............. ...............13....


AB S TRAC T ........._. ............ ...............2_ 1...


CHAPTER


1 POLYLITHIATED SPECIES: APPLICATION TO POLYMER SYNTHESIS .................25

1 .1 Introducti on ............ _... ... ...............25..
1.2 By Reaction with Lithium .................... .. ... ...........................2
1.3 By Reaction of Alkyllithium on Multifunctional Unsaturated Molecules ............._.........26
1.4 By Lithium-Halogen Exchange Reaction............... ...............28
1.5 By Reaction with a Base ........._..._... ...............3. 1...._.....
1.6 Conclusion ........._..._... ...............3. 1...._._....


2 A NOVEL ADDITIVE-FREE DICARBANIONIC INITIATOR FOR THE
SYNTHESIS OF POLY(STYRENE-b-DIENE-b-STYRENE) TRIBLOCK
COPOLYMERS IN NON-POLAR MEDIUM .............. ...............35....


2. 1 Introducti on ................. .... ........ ......... ......... ... .. .........3
2.2 Literature Overview on Symmetric ABA Triblock Copolymers .................. ...............36
2.2.1 Sequential Monomer Addition .............. ...............36....
2.2.2 Coupling of Living AB Chains............... ...............37.
2.2.3 Use of a Difunctional Initiator............... ...............3
2.2.3.1 Divinylbenzene derivatives ....__ ......_____ .......___ ...........4
2.2.3.2 Diphenylethylene-type molecules ....__ ......_____ ..... ......._......4
2.2.3.3 Use of alkali metals ............ ........... ...............43..
2.3 Results and Discussion .............. ...............44....
2.4 Conclusion ................. ...............48....... ......


3 TRI- AND TETRACARBANIONIC INITIATORS BY A LITHIUM/HALIDE
EXCHANGE REACTION : APPLICATION TO STAR-POLYMER SYNTHESIS ...........64


3 .1 Introducti on ................. ..... ..._...... ..... ... ....... ...............6
3.2 Literature Overview on (A)n and (AB)n Star Polymer Synthesis .................. ...............65
3.2. 1"Arm-first" Method ................. .......... .. ...............65....
3.2. 1.1 Use of multifunctional coupling agent ......___ ..... .._._. ........_.._......66
3.2. 1.2 Copolymerization with a divinyl compound ......____ ..... ....___...........73
3.2.2 "Core-first" M ethod............... ......... ..........7
3.2.2. 1 Multifunctional oxanionic initiators ........._..._... ............_...............76











3.2.2.2 Pluricarbanionic initiators .............. ...............77....
3.2.2.3 Polythiolates initiators ................. ...............78................
3.2.3 "In-Out" M ethod .............. ...............78....
3.2.4 "In-In" M ethod ................. ...............80.......... ....
3.3 Results and Discussion ................... .. ..... .. .... .................8
3.3.1 Application of Halogen-Lithium Exchange Reaction to Star Polymer
Synthesis ............ ... .. ..... .. .. ..................................8
3.3.2 Synthesis of Amphiphilic Star Block Copolymers Based on Polybutadiene
and Poly(ethylene oxide) .............. ...............84....
3.4 Conclusion ............ _...... ._ ...............87...

4 TWO-DIMENSIONAL POLYMERIC NANOMATERIALS THROUGH CROSS-
LINKING OF POLYBUTADIENE-b-POLY(ETHYLENE OXIDE) MONOLAYERS
AT THE AIR/WATER INTERFACE ................. ...............106...............

4. 1 Introduction and Literature Overview .................. ... .... ....... ... ........ .............0
4.2 Interfacial Behavior of (PB-b-PEO)n (n = 3 or 4) Star Block Copolymers at the
Air/W ater Interface .............. ... ........... ...............110......
4.2. 1 Surface Pressure-Area Isotherms ................. ......... ......... ............1
4.2.2 Film Relaxation .............. .... .. .. .. ...... .... ...............114.
4.2.3 AFM Characterization of the Transferred Monolayers ................. ... ................ ..1 15
4.3 Cross-linking of Polybutadiene-b-Poly(ethylene oxide) Monolayers at the Air/Water
Interface .................. ............................. .... ......... .......... 1
4.3.1 Interfacial Behavior of (PB-b-PEO)3 Star Block Copolymers ................... ..........119
4.3.2 Reaction of the Polybutadiene Block at the Air/Water Interface in the
Presence of AIBN ............................... .................. ........... ... ... ................... ...... 120
4.3.3 Cross-linking with Hydrosilylated Polybutadiene Blocks at the Air/Water
Interface .............. ... .............. .. .......... 2
4.3.3.1 Application on polybutadiene homopolymer ............ ... ..._.... ........121
4.3.3.2 Application on (PB-b-PEO)3 Star block copolymer ........._..._.._ ................126
4.4 Conclusion ................. ...............133........ ......

5 PLURICARBANIONIC MACROINITIATORS BY A LITHIUM/HALIDE
EXCHANGE REACTION : APPLICATION TO ASYMMETRIC AND MIKTOARM
STAR AND DENDRIMER-LIKE POLYMER SYNTHESIS................ ...............16

5.1 Introduction and Literature Overview ................. ...............163........... ..
5.1.1 Asymmetric and "Miktoarm" Star Polymers .............. ...............163....
5.1.2 Dendrimer-like Polymers ........._.._.. ...._... ...............167..
5.1.2. 1 Introduction to dendrimers ........._.._... ......._ ......_.._ .........16
5.1.2.2 Dendrimers with "true" macromolecular generations .........._....._ .............172
5.2 Results and Discussion .............. .. ........__ ... ......__ ...........17
5.2. 1 Synthesis of Asymmetric and Miktoarm Star Polymers ................ ................. .176
5.2. 1. 1 Introduction of the branching point at the chain end of a linear polymer..177
5.2. 1.2 Preparation of pluricarbanionic macroinitiators for star polymer
synthesis.................. .... ............................. 7
5.2.2 Synthesis of Dendrimer-Like Polystyrene and Polybutadiene ...........................180











5.2.2. 1 Synthesis of star-shaped (G-1) polystyrene and polybutadiene
precursors ............... ......___ .... .__.... .. ..........8
5.2.2.2 Introduction of the branching points at each arm end ............... ..............182
5.2.2.3 Preparation of pluricarbanionic initiators for second generation (G-2)
dendrimer-like polystyrene and polybutadiene synthesis .......................183
5.2.2.4 Third-generation (G-3) dendrimer-like polystyrene and polybutadiene....1 84
5.2.2.5 From the fourth- (G-4) to the seventh-generation (G-7) dendrimer-like
polystyrene synthesis .............. ..... ............ ..........8
5.2.2.6 Viscosity behavior of dendrimer-like polystyrenes .............. .................. 187
5.3 Conclusion ................ ...............189................

6 CONCLUSION AND PERSPECTIVES .............. ...............226....

7 EXPERIMENTAL PART .............. ...............233....

7.1 Purification of Reactants............... ..............23
7.1.1 Solvents .............. ...............233....
7. 1.2 Initiators ................. ...............233...............
7.1.3 A dditives............... .. ........ .. .. ... .. .. .. .. .......23
7. 1.4 Reactants for Halogen-Lithium Exchange and Deprotonation Reactions ............233
7. 1.5 M onom ers ................. .. .. ......... ... ...............235.
7.1.6 Terminating and Functionalization Agent............... .......... .................23
7.2 Preparation of Multibromo Precursors for Pluricarbanionic Initiator Synthesi s............23 5
7.2. 1 Synthesis of Dibromoprecursor for High Performance SBS Triblock
Copolymers .............. .... ...............23 5.
7.2.2 Synthesis of Tribromo Precursor............... ...............23
7.2.3 Synthesis of Tetrabromo Precursor .................... .. .... .............23
7.3 Preparation of a Branching Agent for Dendrimer-Like Synthesis ................ ...............238
7.4 Polymerization and Functionalization .........._..._. ..... ........... .. ........ ....... ........23
7.4.1 Synthesis of High Performance Poly(styrene-b-diene-b-styrene) Triblock
Copolym ers ................. .... ........... .................23
7.4.2 Synthesis of Asymmetric and Miktoarm Star (Co)polymers .............. ..............240
7.4.3 Synthesis of Star (Co)polymers ....._.___ ..... ... .__ ....__ ...........4
7.4.4 Synthesis of Dendrimer-Like Polymers ............... ...............244...
7.5 Two-Dimensional Cross-linking at the Air/Water Interface .............. .....................4
7.5.1 Radical Cross-linking ................. .......... .... .. ..........24
7.5.2 Cross-linking by Self-condensation of Triethoxysilane Groups ..........................246
7.6 Characterization Techniques .............. ...............249....
7.6.1 Elemental Analysis............... ...............24
7.6.2 Gas Chromatography ................. ............... ...............249.....
7.6.3 Size Exclusion Chromatography (SEC) .............. ...............250....
7.6.4 Nuclear Magnetic Resonance (NMR) Spectroscopy..........._._... ......._._.......251
7.6.5 Mass Spectrometry .............. ...............252....
7.6.6 Viscometry .............. ...............252....
7.6.7 Infra-Red Spectroscopy ........._._ ...... .__ ...............253...
7.6.8 Mechanical Properties Analysis .............. ...............253....
7.6.9 Langmuir Films .............. ...............253....











7.6. 10 Atomic Force Microscopy ................. ......... ...............254 ...

LIST OF REFERENCES ................. ...............255................

BIOGRAPHICAL SKETCH .............. ...............28 1...
































































11










LIST OF TABLES


Table page

2-1 Characterization of PS and PB samples synthesized from 1' difunctional initiator. ...............62

2-2 Mechanical properties of SBS triblock copolymers initiated by 1'............. ....................6

3-1 Characterization of PS and PB samples synthesized from 1', 2' and 3' initiators,
respectively. ............. ...............103....

3-2 Characterization of P(S-b-B-b-M)2 pentablock, P(S-b-B-b-M)3 and P(S-b-B-b-M)4 Star
block terpolymer samples. ............. ...............104....

3-3 Characteristics of hydroxyl functionalized (PB-OH)n star polymers and (PB-b-PEO)n (n
= 3 or 4) amphiphilic star block copolymers. ............. ...............105....

4-1 Measurements obtained from isotherm experiments of (PB-b-PEO)4 amphiphilic star
block copolymers. .............. ...............160....

4-2 Characteristics of LB film experiments ................. ...............161..............

4-3 AFM characteristics of (PB-b-PEO)4 four-arm star copolymers............... ................161

4-4 Data for (PB-b-PEO)3 and (PB(Si(OEt)3)-b-PEO)3 Star block copolymers. .........................162

5-1 Characteristics of asymmetric and "miktoarm" star (co)polymers. ............. ....................223

5-2 Characteristics and solution properties of dendrimer-like polystyrenes. ............. ................224

5-3 Characteristics and solution properties of dendrimer-like polybutadienes. ..........................225










LIST OF FIGURES


Figure page

1-1 W urtz coupling reaction. ............. ...............33.....

1-2 Synthesi s of a tricarbanionic initiator. ........._.__...... .___ ...............33.

1-3 Synthesis of polylithiated carbosilane dendrimers. ............. ...............33.....

1-4 Synthesis of pluricarbanionic species from DVB............... ...............34..

1-5 Halogen-lithium exchange reaction ................. ...............34........... ...

1-6 Synthesis of a dicarbanionic initiator from a dibromo precursor. .............. .....................3

2-1 Synthesis of SB S tribock copolymer by sequential monomer addition. ................ ...............49

2-2 Synthesis of SIS triblock copolymer by coupling of living chains on
di chlorodimethyl silane ................. ...............49........... ..

2-3 Synthesis of P(S-b-tBA-b-S) triblock copolymer by coupling of living chains on
b is(b romom ethyl)b enzene ................. ...............50........... ..

2-4 Synthesis of SBS triblock copolymer using 1,3-diisopropenylbenzene as precursor. ............50

2-5 Synthesis of SB S triblock copolymer using 1,3 -di(1 -phenylethenyl)benzene as
precursor. ............. ...............50.....

2-6 Complex diolefinic precursors used for the synthesis of organolithium diinitiators ...............51

2-7 Synthesis of SBS triblock copolymer from a dicarbanionic initiator formed by the
reaction of lithium metal and co-methylstyrene. ....__ ......_____ .......___ ..........5

2-8 Synthesis of P(EO-b-I-b-EO) triblock copolymer from a difunctional initiator formed by
the reaction of potassium metal and naphtalene. ................ ................ ........ ...._..52

2-9 Synthesis of 1-bromo-4-(4' -bromophenoxy)-2-pentadecyl benzene (1). ........._._... ..............53

2-10 1H and 13C NMR spectra (CD2C 2, 400 MHz) of 1-bromo-4-(4' -bromophenoxy)-2-
pentadecyl benzene (1). ............. ...............54.....

2-11 Mass spectrum of 1 -bromo-4-(4'-bromophenoxy)-2-pentadecyl benzene (1). ................... ..55

2-12 Synthesis of a dicarbanionic initiator by halogen-lithium exchange reaction using 1 as
dibromo precursor ....__. ................. .........__..........5

2-13 Secondary reactions resulting from the halogen-lithium exchange reaction.........................56










2-14 1H and 13C NMR spectra (CD2 12, 400 MHz) of the addition product of 1 with sec-
butyllithium obtained after methanolysis............... ..............5

2-15 Mass spectrum of the addition product of 1 with sec-butyllithium obtained after
m ethanolysis. ............. ...............58.....

2-16 Synthesis of a,co-dihydroxy telechelic polybutadiene from 1'. ........._.._.. ........._.._.......58

2-17 SEC eluograms of (PS)2 difunctional polystyrene and (PB)2 difunctional polybutadiene....59

2-18 1H NMR spectrum (CD2 12, 400 MHz) of a,co-dihydroxy terminated polybutadiene. ........60

2-19 13C NMR spectrum (CDCl3, 400 MHz) of a a,co-dihydroxy terminated polybutadiene...... .60

2-20 Synthesis of SBS triblock copolymer from 1'. ............ ...............61.....

2-21 SEC eluograms monitoring the formation of a SBS triblock copolymer initiated in
cyclohexane with 1' ....___ ............... ................ ........ ......... ........ .61

2-22 1HNMR spectrum (CDCl3, 400 MHz) of a SBS triblock copolyme................ ...............6

3-1 General strategies for star polymer synthesis. ............. ...............88.....

3-2 Convergent method............... ...............89.

3-3 Reaction of polymer chains with a difunctional monomer. .........____........._._ ........._...89

3-4 Synthesis of a coupling agent with 18 chlorosilane functions............... ...............8

3-6 Anionic synthesis of 4-arm star branched polystyrene using 1,2-
bis(dichloromethyl silyl)ethane as functionalizing agent. ................ ................. ........ 90

3-7 Halogen-lithium exchange reaction ................. ...............90................

3-8 Synthesis of 4-arm star branched polymers using tetrabromomethylbenzene as linking
agent. .............. ...............90....

3-9 Synthesis of PI star polymer using HFPO as multifunctional coupling agent. ........._.._..........90

3-10 Use of 1,3,5-tris(1 -phenylethenyl)benzene as coupling agent. ................ ............. .......91

3-1 1 Use of fullerene C60 aS linking agent for star polymer synthesis. ................ ............... .....91

3-12 Divergent method. ............. ...............91.....

3-13 Synthesis of three-armed poly(propylene sulfide) star. ....._____ .... ... .__ ........_.._.....92

3-14 Synthesis of four-arm PS star by the "In-Out" method. ................................... 9










3-15 Application of the "In-In" method for star synthesis. ............. ...............93.....

3-16 Synthesis of dilithiated (1'), trilithiated (2'), and tetralithiated (3') initiators.............._.._.. ...93

3-17 Scheme of the tetracarbanionic initiator/lithium 2-methoxyethoxide o-C1 complex. ............94

3-18 Synthesis of four-armed polystyrene stars. ................ ............... ......... ........ ...94

3-19 SEC eluograms of (PS)4 pOlystyrene and (PB)4 pOlybutadiene stars ................. ...............95

3-20 1H NMR spectra (CD2 12 ; 400MHz) of (PB-OH)4 and (PB-OH)3 hydroxyl terminated
star polym ers. .............. ...............96....

3-21 Reaction scheme for the synthesis of SBM star block terpolymers. ............. ...................97

3-22 SEC eluograms monitoring the formation of a P(S-b-B-b-M)2 pentablock copolymer. .......97

3-23 SEC eluograms monitoring the formation of a P(S-b-B-b-M)n (n = 3 or 4) star block
terpolym er. .............. ...............98....

3-24 1H NMR spectrum (CDCl3, 400 MHz) of P(S-b-B-b-M)3 Star block terpolymer. ...............99

3-25 Synthesis of (PB-b-PEO)4 Star block copolymers. ............. .....................100

3-26 1H NMR spectra (CDCl3 ; 400MHz) of a star copolymer (PB76-b-PEO444)4 ...................... 101

3-27 SEC traces of the (PB-OH)4 preCUTSor and of the star copolymers (PB76-b-PEO,,)41H
TH F. ............. ...............101....

3-28 1H NMR spectra (200MHz) of (PB76-b-PEO444)4 in CD2 12 (A) and in CD30D (B).........102

4-1 Direct visualization of the 1% unreacted (A) and 0.05% cross-linked (B) wormlike
micelles of PB45-b-PEOss diblock copolymer by cryotransmission electron microscopy. ...134

4-2 Formation and osmotic deflation of PB46-b-PEO26 diblock copolymer, vesicles either
without (A, B) or with (C) cross-linking between the hydrophobic segments of
butadiene. .............. ...............134....

4-3 Representation of the concept of a two-dimensional network of molecular pores, i.e.,
perforated monol ay ers" ................ ................. 13......... 5....

4-4 A quasilinear coupler (a, p-xylylene dibromide), a cross-shaped monomer (b, lanthanum
sandwich complex of tetrapyridylporphyrin), an idealized structure (c), and an STM
image (d) of a square grid. .......................... ........135

4-5 Amphiphilic porphyrins Pi and P2. Pi: R = R1 (M = H2, Cu); P2: R = R2 (M = H2, CU,
Fe). Amphiphilic porphyrazine P3 (M = Cu). ............. ...............136....

4-6 General reactions involved in the polymerization of alkoxysilanes ................. .................1 36










4-7 Molecular structure of the lipopolymer polymerized by exposure to UV light. ...................137

4-8 Surface Pressure-Area per polymer molecule isotherms at 298K for (PB76-b-PE0n)4 Star
block copolymers (n = 57, 137, 444 and 1725). ............. ...............137....

4-9 Isotherm of (PB76-b-PEO444)4 depicting how measurements of molecular area for the
three principal regions are obtained. ............. ...............138....

4-10 Linear dependence of A, on the total number of ethylene oxide units. .........._...._ ..............138

4-1 1 Linear dependence of AApseudoplateau On the total number of ethylene oxide units. ..............139

4-12 Compression/expansion curves for two different samples of PB4-b-PEO4 Star block
copolymers ((PB76-b-PE057)4 and (PB76-b-PE057)4) at (A) 5 mN.m l, (B) 10mN.ml
and (C) 15mN.m l. ........... ...............140.....

4-13 Evolution of transfer ratio with the surface pressure in the case of (PB76-b-PE0l725)4
star block copolymer sample. ............. ...............141....

4-14 AFM tapping mode amplitude images of the (PB76-b-PE0l725)4 (A, B, C, D, E, F, G
and H) and (PB76-b-PE057)4 (I and J) star block copolymers transferred to a mica plate
support at various surface pressures.. ............ ...............142.....

4-15 Dependence of the number of molecules per domain on the surface pressure in the case
of the (PB76-b-PE0l725)4 Star block copolymer sample. The general trend shows that as
pressure increases, more molecules aggregate (dramatic increase from TI= 4 mN/m) to
form the observed circular PB microdomains. ............. ...............143....

4-16 Model proposed to explain the formation of a network of elongated stripes.. .................... 144

4-17 Surface Pressure-Area per polymer molecule isotherms for (PB200-b-PE0n)3 Star block
copolymers (n = 76, 326, 970, and 2182). ................ ......... ....... .. ........4

4-18 Linear dependence of AApseudoplateau On the total number of ethylene oxide units. ..............145

4-19 Surface Pressure-Area isotherms for (PB200-b-PEO76)3 Star block copolymer before and
after cross-linking in the presence of AIBN under UV light (x: = 20 mN/m) ................... ..146

4-20 IR spectra of (PB200-b-PEO76)3 before and after cross-linking in the presence of AIBN
under UV light. ............. ...............146....

4-21 AFM topographic images of the (PB200-b-PEO76)3 Star block copolymer transferred to
mica substrates (n: = 20 mN/m) before (A) and after cross-linking (B, C, D, and E) at
different reaction times.. ............ ...............147.....

4-22 Hydrosilylation of the pendant double bonds of the PB homopolymer. ............. .............148

4-23 1H NMR spectrum (CDCl3 ; 300MHz) of the commercial linear polybutadiene.............._148










4-24 1H NMR spectrum (CDCl3 ; 300MHz) of the hydrosilylated polybutadiene. ..................149

4-25 IR spectra of the polybutadiene before and after hydrosilylation. ........._._ .........._.......149

4-26 Cross-linking reaction involving hydrolysis and condensation of the triethoxysilane
groups of the polybutadiene backbone. ............. ...............150....

4-27 Surface pressure-Mean Molecular Area isotherms of the hydrosilylated polybutadiene
carried out after different reaction times (sub phase pH = 3.0). ............. .....................15

4-28 Static elastic modulus-surface pressure curves of the hydrosilylated polybutadiene at
different reaction times (subphase pH = 3.0) ................. ...............151.....___ .

4-29 Mean Molecular Area-Time isobars of the hydrosilylated polybutadiene for various
subphase pH values (n: = 10 mN/m). ............. ...............151....

4-30 Removal of the cross-linked homopolymer from the Langmuir trough surface ........._......152

4-3 1 AFM topographic images of the LB films transferred onto mica substrates at n: = 10
mN/m: the commercial polybutadiene (A) and the hydrosilylated polybutadiene at pH
= 7.0 (B; t = 0 h) and 3.0 for different reaction times (C ; t = 20 min and D; t = 10 h).
(E and F) Cross-section analysis of the images C and D ......___ ... .....__ .............152

4-32 Hydrosilylation of the pendant double bonds of the (PB-b-PEO)3 Star block copolymer...153

4-33 1H NMR spectra (CDCl3 ; 300MHz) of (PB200-b-PEO326)3 Star copolymer and the
corresponding hydrosilylated (PB78-co-PB(Si(OEt)3)122-b-PEO326)3 Star block
copolym er. ............. ...............154....

4-34 IR spectra of the (PB200-b-PEO326)3 Star block copolymer and the corresponding
hydrosilylated (PB78-co-PB(Si(OEt)3)122-b-PEO326)3 Star block copolymer. .....................155

4-35 Surface Pressure-Area isotherms for (PB200-b-PEO326)3 Star block copolymer and the
corresponding hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star block copolymer before (pH
= 3.0, t = Oh) and after (pH = 3.0, t = 10h) cross-linking. ............. ......................5

4-36 Surface pressure-Area isotherms (A) and Compressibility-Area curves (B) for the
hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star block copolymer carried out at different
reaction times (subphase pH = 3.0). ............. ...............156....

4-37 Isobars of the hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star block copolymer for various
subphase pH values (n: = 5 mN/m). ............. ...............157....

4-3 8 Removal of the cross-linked (PB(Si(OEt)3)-b-PEO)3 Star copolymer from the Langmuir
trough surface. The dark yellow material easily comes off the subphase using a
spatula. ............. ...............157....










4-39 AFM topographic images of the (PB(Si(OEt)3)-b-PEO)3 Star block copolymer LB fi1ms
transferred to mica substrates at subphase pH = 7.0 (A; t = 0 h) and 3.0 for different
surface pressures (B, C, D, E, F, G and H; t = 10 h) .............. ...............158....

4-40 AFM section analysis of the images of the (PB(Si(OEt)3)-b-PEO)3 Star block
copolymer LB fi1ms transferred to mica substrates at subphase pH 3.0 for different
surface pressures (t = 10 h). ............. ...............159....

4-41 AFM topographic images of the (PB(Si(OEt)3)-b-PEO)3 Star block copolymer LB fi1ms
transferred to mica substrates at subphase pH = 3.0 (t = 10 h) before (n: = 9 mN/m) and
after (n: = 2 mN/m) expansion of the monolayer. ................ ...............159........... .

4-42 Surface Pressure-Area isotherms for the hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star
block copolymer cross-linked at subphase pH 3.0 (t = 10 hrs) for two different surface
pressures (n: = 5 and 20 mN/m). ............. ...............160....

5-1 Representative structures of asymmetric and "miktoarm" star polymers. ............................190

5-2 Synthesis of three-arm asymmetric PS star using chlorosilane as linking agent. ..................1 91

5-3 Synthesis of (PS)2-b-P2VP miktoarm star copolymer by combination of linking and
hydrosilylation reactions. ................. ...............191........ ......

5-4 Synthesis of asymmetric PS star using DDPE derivative as coupling agent.............._.._. .....191

5-5 Use of DPE derivative as branching agent. ........._.. ....._.._ ...._._ ......._.... ....192

5-6 Representation of different tree-like macromolecular structures. ............. .................... 193

5-7 Representation of dendrimer growth by the divergent and convergent methods. ........._......194

5-8 Synthetic route developed by Voigtle for the synthesis of branched polyamides. ...............194

5-9 Synthetic route for the preparation of PAMAM dendrimers by the divergent method.........195

5-10 Synthesis of poly(ether amide) dendrimers ................. ......... ......... ...............196

5-11 Synthesis of poly(benzyl ether) dendrimers by the convergent method. .................. ..........197

5-12 Synthetic strategy toward dendrimer-like PEO. ............. ...............198....

5-13 Synthesis of dendrimer-like copolymers PS3-b-PEO6 .....__.___ ..... ... ._ .................1 99

5-14 Synthesis of a second-generation dendrimer-like PS by ATRP. ............. ....................20

5-15 Synthesis of a third-generation dendrimer-like poly(L-lactide). ............. ....................20

5-16 Functionalization of PMMA star chain ends by a TERMINI compound. ................... ........202










5-17 Divergent iterative synthetic strategy elaborated for synthesis of dendritic PMMA by a
combination of LRP and TERMINI. ............. ...............203....

5-18 Synthesis of a second-generation dendritic P(S2I3) COpolymer .................... ...............20

5-19 General reaction scheme for the synthesis of third-generation dendritic PB. ....................204

5-20 Synthesis of second-generation dendrimer-like PS by coupling reaction of living chains
on chlorosilane star chain ends. ............. ...............205....

5-21 Synthesis of second-generation dendrimer-like star-branched PMMA. ............. ................206

5-22 SEC trace (RI detector) of polystyryllithium living chains after reaction with 4,4'-
dibromodiphenylethylene .............. ...............206....

5-23 Synthesis of asymmetric and "miktoarm" star (co)polymers. .............. ...................20

5-24 SEC traces (RI detector) of PS(Br)2 aryl bromide-terminated polystyrene and its
precursor PS-OH hydroxyl-terminated polystyrene. ............. ...............208....

5-25 1H NMR spectra (CD2 12; 400 MHz) of PEO(Br)2 aryl bromide-terminated
poly(ethylene oxide) and its precursor PEO-OH hydroxyl-terminated poly(ethylene
oxide) .............. ...............209....

5-26 1H NMR spectra (CD2 12; 400 MHz) of PB(Br)2 aryl bromide-terminated
polybutadiene and its precursor PB-OH hydroxyl-terminated polybutadiene .................210

5-27 SEC traces (RI detector) of asymmetric star polystyrenes PS-b-PS2 and its precursor
P S-(B r)2 ................. ...............211........... ...

5-28 SEC traces (RI detector) of asymmetric star polymer PB-b-PB2 and "miktoarm" star
copolymer PB-b-PS2 and its precursor PB-(Br)2 ................. ...............211..............

5-29 SEC traces (RI detector) of "miktoarm" star copolymers PS-b-PB2, PS-b-PI2, and its
precursor PS-(Br)2 ................. ...............212................

5-30 1H NMR spectrum (CD2 12; 400 MHz) of an asymmetric star polybutadiene PB-b-
PB2z(OH)2 ................ ...............213................

5-3 1 Synthesis of third-generation dendrimer-like polystyrene. ................ ............... ...._..214

5-32 SEC traces (RI detector) of PS4(Br)s and PB4(Br)s aryl bromide-terminated polystyrene
and polybutadiene stars and its precursors (PS-OH)4 and (PB-OH)4 hydroxyl-
terminated polystyrene and polybutadiene stars and the tetrabromoinitiator. ....................215

5-33 1H NMR spectrum (CD2 12; 400 MHz) of (PB-OH)4 hydroxyl-terminated
polybutadiene star ...........__..... .___ ...............216....










5-34 1H NMR spectra (CD2 12; 400 MHz) of PB4(Br)s aryl bromide-terminated
polybutadiene star. .............. ...............216....

5-35 SEC traces (RI detector) of dendrimer-like polystyrenes............... .............21

5-36 SEC/HT traces (RI detector) of (A) dendrimer-like polystyrenes and (B) dendrimer-like
polybutadienes .............. ...............218....

5-37 1H NMR spectrum (CD2 12; 400 M~z) of a hydroxyl-terminated dendrimer-like
polybutadiene PB4-b-PBs(OH)s. .............. ...............219....

5-38 1H NMR spectrum (CD2 12; 400 M~z) of a aryl bromide-terminated dendrimer-like
polybutadiene PB4-b-PBs(Br)16 .............. ...............220....

5-39 Evolution of the hydrodynamic radius (RH) aS a function of the number of generation
(G) for dendrimer-like polystyrenes prepared using tetrafunctional .............. .................221

5-40 Evolution of Log[ r] as a function of the number of generation (G) for dendrimer-like
polystyrenes prepared using tetrafunctional .............. ...............221....

5-41 Evolution of Log[r] as a function of Log Mn for dendrimer-like polystyrenes prepared
from tetrafunctional .............. ...............222....

6-1 Conceivable tetracarbanionic initiator. ........._.__ .......... ...............228.

6-2. Synthetic strategy proposed for brush polymer preparation ................. .......................228

7-1 Synthesis of 1-pentadecyl-3-phenoxy benzene. ............. ...............255....

7-2 Synthesis of 1,3,5-tri s(4-bromophenyl)benzene ................. ...............255........... .

7-3 Synthesis of 1,3 -bis(p-bromophenyl)-2-propane ................. ...............255..............

7-4 Synthesis of 2,3,4,5-tetrakis(p-bromophenyl)-cyclopentadinon............... ................. .255

7-5 Synthesis of (1,2,3 ,4-tetrabromophenyl)-5-phenyl)benzene. ................ .......................256









Abstract of Dissertation Presented to the Graduate School
of the University of Florida and the University of Bordeaux 1 in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

APPLICATION OF LITHIUM/HALIDE EXCHANGE REACTIONS TO THE SYNTHESIS
OF COMPLEX POLYMER ARCHITECTURES: INVESTIGATION OF THEIR
SELF-ASSEMBLING PROPERTIES AT THE AIR/WATER INTERFACE

By

Rachid Matmour

August 2007

Chair: Randolph S. Duran
Major: Chemistry

An entire set of hydrocarbon-soluble polycarbanionic initiators and macroinitiators was

synthesized by using a simple halogen-lithium exchange reaction (Gilman's reaction) carried out

on multibromo molecule and macromolecule precursors. Using these multicarbanionic

(macro)initiators an entire set of complex polymer architectures has been synthesized by anionic

polymerization using a divergent method.

This strategy was first applied to the preparation of simple polymer architectures such as

poly(styrene-b-butadiene-b-styrene) triblock copolymers with excellent mechanical properties,

obtained using a new hydrocarbon soluble dicarbanionic organolithium initiator containing a side

Cls-alkyl chain.

The same exchange reaction has been successfully applied to generate tri- and

tetracarbanionic species from tris- and tetrakis-bromoaryl compounds. The use of a o/C1 ligand

was instrumental in obtaining polycarbanionic initiators soluble in apolar medium, and the

subsequent preparation of various well-defined three and four-armed polystyrene and

polybutadiene stars synthesized by the "core-first" method. The efficiency of the latter was even

exploited to synthesize poly(butadiene-b-ethylene oxide) (PB-b-PEO),, amphiphilic star block










copolymers and poly(styrene-b-butadi ene-b-methyl methacrylate) (P(S-b-B -b-M),) star bl ock

terpolymers (n = 3 or 4).

The potential of PB-b-PEO star block copolymer to self-assemble at the air/water

interface was exploited to synthesize a two-dimensional polymeric nanomaterial consisting of a

continuously cross-linked polybutadiene two-dimensional network with poly(ethylene oxide)

domains of controlled sizes trapped within the network. To reach that goal, novel (PB(Si(OEt)3)-

b-PEO)3 Star block copolymers were designed by hydrosilylation of the pendant double bonds of

(PB-b-PEO)3 Star block copolymer precursors with triethoxysilane. Self-condensation of the

triethoxysilane groups under acidic conditions led to a successful cross-linking of the

polybutadiene blocks directly at the air/water interface without any additives or reagents.

Finally, the Gilman reaction was extended on m,o'-dibromo chain-end polymers after the

introduction of a branching agent whose halogen atoms are carried by separate aryl rings to

afford hydrocarbon-soluble polycarbanionic macroinitiators. This provided an efficient synthetic

route to the asymmetric and "miktoarm" star (co)polymers based on the combination of different

polymers such as polystyrene, polybutadiene, and polyisoprene. By the reiteration of this

sequence of reactions (branching and halogen-lithium exchange reactions) starting from a

tetrafunctional initiator, dendrimer-like PS and PB up to the seventh and third generations,

respectively, could be successfully synthesized.











Resume du rapport de these presented aux ecoles doctorales
de l'Universite de Floride et de l'Universite Bordeaux 1
pour l'obtention du grade de Docteur

APPLICATION DE REACTIONS D'ECHANGE HALOGENE/LITHIUM A LA SYNTHESE
DE POLYMERES A ARCHITECTURES COMPLEXES. ETUDE DE L'AUTO-
AS SEMBLAGE A L'INTERFACE AIR/EAU

par

Rachid Matmour

Decembre 2006

President de la commission d'examen: Randolph S. Duran
Specialite : Chimie des polymeres

Une nouvelle famille d'amorceurs et de macroamorceurs pluricarbanioniques solubles en

solvant apolaire a ete synthetisee par une reaction d'echange halogene-lithium (reaction de

Gilman) effectuee sur des composes halogenes (macro)moleculaire. L'utilisation de ces especes

pluricarbanioniques comme (macro)amorceurs a permis la synthese de differentes architectures

polymeres complexes par polymerisation anionique par voie divergente.

Cette strategie a tout d'abord ete appliquee a la preparation d'architectures polymeres

simples telles que des copolymeres triblocs poly(styrene-b-butadie~ne-b-styrene), aux proprie~tes

mecaniques interessantes, obtenus a l'aide d'un amorceur dicarbanionique soluble en milieu

apolaire et ce sans additif grace a l'ajout d'une chaine alkyle de 15 carbones sur la structure de

l'amorceur.

Cette mime reaction d'echange halogene-lithium a ete appliquee a la preparation

d'especes tri- et tetracarbanioniques a partir de composes tri- et tetrabromoaryl. Dans ce cas,

I'utilisation de ligand o/C a neanmoins ete necessaire pour l'obtention d'amorceurs

multicarbanioniques solubles en milieu apolaire et la preparation de polystyrene et de

polybutadiene en etoile a trois et quatre branches synthetisees par la methode << core-first >>.










L'efficacite de ces especes pluricarbanioniques a aussi ete exploitee pour la synthese de

copolymeres diblocs amphiphiles en etoile poly(butadiene-b-oxyde d'ethylene) et de

copolymeres triblocs en etoile poly(styrene-b-butadie~ne-b-methacrylate de methyle) a troi s et

quatre branches.

L'interit potential d'architectures polymeres tels que les copolymeres amphiphiles en

etoile poly(butadiene-b-oxyde d'ethylene) a l'interface air/eau a pu 6tre demontre a travers la

synthese de nanomateriaux polymeres bidimensionnels bases sur un reseau en deux dimensions

de polybutadiene reticule possedant des domaines de poly(oxyde d'ethylene) de tailles contr81ees

pieges au sein du reseau. Pour atteindre cet objectif, les blocs de polybutadiene ont d'abord ete

fonctionnalises par des groupements triethoxysilane apres hydrosilylation des doubles liaisons

pendantes du copolymere en etoile poly(butadiene-b-oxyde d'ethylene). La condensation des

groupements pendants triethoxysilane sous conditions acides a ainsi permis la reticulation des

blocs polybutadiene directement a l'interface air/eau.block copolymers and poly(styrene-b-

butadiene-b-methyl methacrylate) (P(S-b-B-b-M)n) star block terpolymers (n = 3 or 4).

L'utilisation de la reaction de Gilman a finalement ete etendue a la preparation de

macromamorceurs pluricarbanioniques solubles en milieu apolaire a partir de chaines polymeres

possedant un groupement dibrome en extremite de chaine, apres l'introduction d'un agent de

branchement dont les atomes d'halogenes sont portes par deux noyaux aromatiques differents.

Cette methode a permis l'elaboration de (co)polymeres en etoile asymetriques et << miktoarms >>

constitutes de polystyrene et polydienes. La repetition de cette sequence de reactions

(branchement et reaction d'echange halogene-lithium) en partant d'un amorceur tetrafonctionnel

a ainsi amene a la synthese de dendrimeres de polystyrene de septieme generation et de

polybutadiene de troisieme generation.









CHAPTER 1
POLYLITHIATED SPECIES: APPLICATION TO POLY1VER SYNTHESIS

1.1 Introduction

For many years it was thought by organic chemists that it was impossible to prepare

polylithium organic compounds defined as organic compounds containing two or more lithium

on the same or adjacent carbons. It was widely believed that having two lithiums on the same or

adjacent carbon atoms would lead to a destabilization and lithium hydride elimination. This

misconception was changed in the early 1970s by work of Westl and Lagow.2 Actually, there are

four distinct methods to quantitatively convert a multifunctional compound to polylithiated

species.

1.2 By Reaction with Lithium

The reaction with lithium metal or vapor on different categories of molecules such as

alkanes, alkenes, aromatics, or also alkyl and aryl halide was the first synthetic method

discovered for the preparation of polylithium organic compounds. The use of lithium metal,

notably used for the synthesis of butyllithium, was first reported in the early 1950s by West et

al~l34 with the conversion of 1,5-dichloropentane to 1,5-dilithio compound. This strategy was

later developed by the Lagow group5-13 with the reaction at high temperature of lithium vapor

with halogenated organic compounds as a general synthesis for polylithium compounds.

However, extremely low yield reactions with a mixture of compounds avoid any

purification or characterization of the pure product. This very low yield is explained first by ot-

lithium-halide elimination occurring from molecules having a halide and a lithium on the same or

adj acent carbons producing carbenes and lithium halides. Furthermore, the reaction of lithium on

the halide compound is in competition with a secondary reaction of intermolecular coupling

reaction between the lithiated species and the alkyl halide reagent (Wurtz coupling)14 (Figure 1-









1) which has no serious consequence for a monofunctional initiator, but not for the case of

pluricarbanionic compounds.

1.3 By Reaction of Alkyllithium on Multifunctional Unsaturated Molecules

The most recent method is based on the reaction of alkyllithium on the unsaturations of a

multifunctional agent. This strategy was first applied for the synthesis of dilithiated compounds

by reaction of butyllithium on difunctional unsaturated reagents such as divinylbenzene (DVB)

derivatives,15,16 Or double diphenylethylene (DDPE) derivatives.17-19 The latter dilithiated species

were actually used, as shown below (Chapter 2), for the preparation of poly(styrene-b-butadi ene-

b-styrene) (SBS) triblock copolymers. By using this strategy, only one group was successful in

the preparation of pluricarbanionic species of functionality higher than 2. Indeed, Quirk and

Tsai20 Synthesized tricarbanionic species, soluble in apolar solvents by reaction of 3 moles of

sec-butyllithium with 1,3,5-tris(1 -phenylethenyl)benzene (tri-DPE) as presented in Figure 1-2.

This hydrocarbon-soluble initiator was found to be efficient for the anionic polymerization of

styrene, but only when THF was also added in the reaction mixture ([THF]/[Li] = 20). The

addition of THF as a polar additive modified the aggregation rate of the pluricarbanionic species

and gave by the same way a quantitative initiation.

The same initiator was also used to produce three-arm polybutadiene stars.21 Even though

a complete monomer consumption was observed, the size exclusion chromatography (SEC)

analysis showed a bimodal distribution. This behavior was attributed to the strong aggregation

effects of the trifunctional initiator in a non polar solvent. The problem was overcome when s-

BuOLi was added in the reaction mixture in a ratio [s-BuOLi]/[Li] = 2. s-BuOLi was shown to

be capable of disrupting the initiator association without affecting appreciably the microstructure

of the polybutadiene chains.









The limitations of the method include the extreme care that should be exercised over the

stoichiometry of the reaction between s-BuLi and tri-DPE to avoid the presence of a second

population of linear polymers or the formation of initiators of lower functionality and the fact

that a minimum arm molecular weight of around 6.103 g.mOl-1 is required for the growth of the

polymer chains on the three carbanionic sites at the same time.

By the same manner, the Moiller group22 employed polylithiated carbosilane dendrimers,

as multifunctional initiator (Figure 1-3). The dendrimers had 16 or 32 allyl groups at their

periphery. A hydrosilylation route was performed to react half of these terminal allyl groups with

didecylmethylsilane (Figure 1-3). The remaining allyl groups were lithiated by the addition of s-

BuLi, to produce the multifunctional initiators. These initiators carrying theoretically 8 or 16

carbionic sites were soluble in polar solvents (THF) and were subsequently used for the

polymerization of styrene, ethylene oxide, and hexamethylcyclotri siloxane (D3). The polymer

stars obtained demonstrated a monomodal molecular weight distribution. However, molecular

weight characterization data were not provided in this study and the number of branches for

these stars was not determined, thus leaving uncertain the formation of the desired structures.

Parallel to these pluricarbanionic species of precise functionality, many research groups

worked on the synthesis of multifunctional initiators most certainly less well-defined, but

allowing the access to star polymers with a very high number of branches. First demonstrated by

Eschwey et al 23,24 and later developed by Rempp and colleagueS25,26 DVB was polymerized by

butyllithium or naphtalene lithium in benzene at high dilution to obtain a stable microgel

suspension. These heterogeneous microgel nodules, which were described as "living" microgel

nodules covered by living anionic sites (for example, by using a ratio of [DVB]/[BuLi]=2, a

microgel with a molecular weight of2n = 1.9 x 103 g.mOl-1 and a polydispersity of 16.8 could be









obtained)24 (Figure 1-4), were subsequently used as multifunctional initiators to polymerize

styrene, isoprene, or butadiene. However, it should be noted a relatively bad control over the star

functionality since it is impossible to predict the number of branches using this method.

A slight variation was adopted by Okay and Funke27,28 The polymerization of DVB was

initiated by living poly(tert-butyl styryl)1ithium chains having low molecular weights in order to

avoid the solubility problems arising from the strong association of the carbon-lithium functions

in the nonpolar solvent. By using this strategy, Rempp and colleagueS26 Synthesized poly(tert-

butyl acrylate) (PtBuA) and poly(ethylene oxide) (PEO) stars. The synthesis was performed in

THF to minimize the strong association effects, using naphtalene lithium or cumyl potassium to

polymerize DVB for the PtBuA or PEO star synthesis, respectively. DVB polymerization was

initiated by electron-transfer instead of by addition. The polymerization of tBuA was carried out

at -55 oC in the presence of LiCl after the active centers have been reacted with a suitable

amount of 1,1 -diphenylethylene (DPE) to reduce their nucleophilicity. It was found that the mole

ratio [DVB]/[Li ] should vary between 1.5 and 2.5 to afford a stable microgel suspension. The

molecular characteristics of the final products and the calculated molecular weight of the

branches determined by SEC and light scattering (LS) revealed the existence of multimodal

molecular weight distribution with large numbers of arms, ranging from 22 to 1300 and from 5

to 219 for the PtBuA or PEO stars, respectively.

1.4 By Lithium-Halogen Exchange Reaction

The third method based on the exchange reaction between a halide and a metal described

by Gilman et al.29 is one of the most used methods for the preparation of aryllithium species. It

consists in the reaction of an aryl halide, such as bromobenzene, with an alkyllithium, typically

butyllithium (Figure 1-5).29,30 This equilibrated reaction is strongly displaced to the most stable

lithiated compound and was described as quantitative under certain conditions. The Wurtz









coupling reaction (Figure 1-1), non negligible in the case of alkyl bromides, does not happen in

the case of aryl bromides due to the low nucleophilicity of phenyllithium toward the bromide

compounds.14

Thus, Lagow and colleagueS31,32 USed this halogen-lithium exchange reaction notably for

the synthesis of hexalithiobenzene from the hexachlorobenzene, but with a relatively low yield

(53%).

By the same manner, some other groups took advantage of this halogen-lithium exchange

reaction for molecule functionalization. Kleij et al.33 developed a useful synthetic procedure for

the incorporation of the potentially multidentate monoanionic ligands via the para-position on the

periphery of carbosilane dendrimers. Dendritic carbosilanes functionalized with (N)CNPh-Br

end groups could be selectively lithiated in presence of t-BuLi in Et20 to give their multilithiated

aminoaryl derivatives with stable C-Li bonds which were used to introduce various metals such

as Pt via lithiation/transmetalation sequences.

Jayaraman and Nithyanandhan34 prOposed also another example of dendrimer

functionalization through an efficient halogen-lithium exchange reaction. Poly(alkyl aryl ether)

dendrimers were functionalized with bromophenyl groups at their periphery so as to have 3, 6,

12, and 24 groups in the zero, first, second, and third generation dendrimers, respectively. The

bromophenyl functionalized dendrimers were converted quantitatively to their polylithiated

derivatives by reaction with n-BuLi in benzene. Although the polylithiated dendrimers

precipitated as a white solid, they were reacted either with D20 or with CO2, So as to afford the

corresponding deuterated and carboxylic acid functionalized dendrimers, respectively. The

carboxylic acid functionalized dendrimers were modified further to methyl esters during their

characterization.









The Saa group35 prOposed the generation of polylithiated derivatives of salicylic and

oligosalicylic acids soluble in THF by means of the halogen-metal exchange reaction from

bromo-substituted salicylic and oligosalicylic acids, including some with base-sensitive chiral

centers avoiding the need to use protecting groups. These polylithiated species were notably used

for the introduction of specific functions (-SMe, -CH(OH)C6HS, or -C(=0)OEt) under these

conditions.

More recently, a two-step synthetic procedure towards coil-rod-coil triblock copolymers

was developed by Tsitsilianis et al.36 In the first step, ot,co-oligophenylenes (rod part) were

modified by halogen-lithium exchange reaction to anionic bifunctional initiators soluble in THF

(Figure 1-6). In the second step, flexible chains were grown from both ends of the rod part by an

anionic polymerization procedure leading to polystyrene-rod-polystyrene and/or poly(2-vinyl

pyridine)-rod-poly(2-vinyl pyridine) triblock copolymers.

It should be noticed that the yield of the halogen-lithium exchange reaction depends on

different experimental parameters such as the concentration in bromide compound, the nature of

the solvent, the temperature and the nature of the alkyllithium agent used.37-41 Although n-BuLi

was the most used until now, Tsitsilianis et al.36 demonstrated that the reaction is quantitative in

presence of s-BuLi for the aryl bromide compounds. t-BuLi is rather used for the iode/lithium

exchange reaction.42 The concentration of the bromo precursor [Ar-Br] = 5.3.10-2 mOl.L^1 was

found by Trepka and Sonnenfeld40 to be the most appropriate for a good conversion to

phenyllithium species (> 95%). The exchange reaction could be done either in apolar40 Or polar

solvents,29 the most appropriate being the one in which the polylithiated compound is soluble.

However, in the case of polar solvents the reaction should be done between -40 and -100 oC

because of the low stability of the lithiated species in polar solvents such as THF or dimethyl









ether. Indeed, lithiated compounds could react with ether functions to form by cleavage reaction

alkene and lithium alkoxide.14 In the case of apolar solvents such as cyclohexane or benzene, the

reaction could be done at room temperature with no limitation in term of temperature.

1.5 By Reaction with a Base

The last method was less used with only a few cases proposed. This method consists in

removing an acidic proton by metalation or with the help of a base. For example, Fujimoto et

al.43 were successful in preparing a soluble pluricarbanionic initiator in a mixture of

THF/diglyme by reaction of 1 ,3 ,5-tri s-(u-methoxyb enzyl)b enzene and a mixture of

sodium/potassium. However, this trifunctional initiator was not able to quantitatively initiate the

polymerization of a-methylstyrene leading to a mixture of linear chains, dimer species, and star

polymers. Hogen-Esch and colleagueS44 also proposed the synthesis of a trifunctional initiator by

metalation of 1,3,5-tris[2-(2' -pyridyl)ethyl]benzene in presence of a,co-dipotassio-a-

methylstyrene. Used as initiator for the polymerization of 2-vinylpyridine and 4-vinylpyridine in

THF, the latter compound leads to polymer samples with large molecular weight distribution and

residual initiator. Studies of the reaction of bases on trimethylbenzene have shown the formation

of a mixture of mono-, di-, and trilithiated species under these conditions. Although the use of a

Lochmann base by Gordon et al.45,46 allowed the formation of pure tricarbanionic species by

trimetalation of 1,3-cycloheptadiene in pentane, no interest was found in this polylithiated

species as initiator for the polymerization.

1.6 Conclusion

The reasons that are generally held responsible for polylithiation to be impractical--

especially when the halogens to be substituted happened to be on the same carbon or on adj acent

carbons--are two-fold. a-Lithium-halide eliminations and intermolecular couplings between the









lithiated reagent and the halide-substituted species are two important competing reactions that

have long prevented polylithiation reactions from being practically considered. Another reason

for the little attention given to multiple metal-halide exchanges is because polylithiated

compounds exhibit limited solubility in most organic solvents, forming rather insoluble

aggregates of little utility. Added to the previous complications, different requirements have to

be fulfilled by a multifunctional initiator in order to produce polymers with uniform arms, low

molecular weight distribution, and controllable molecular weights. All the initiation sites must be

equally reactive and have the same rate of initiation. Furthermore, the initiation rate must be

higher than the propagation rate.

For instance, in polymer chemistry polylithiation has never been contemplated for the

reasons mentioned above; had it been mastered and the experimental conditions worked out

polylithiation would be a viable and straightforward route to prepare multicarbanionic initiators

for the subsequent synthesis of star-shaped polymers. So far the only possibility of generating

such multicarbanionic initiators was lithiation by addition to multivinyl compounds, but the very

small number of reports on this strategy of synthesis indicates that it is not that convenient a

route. It indeed requires the prior synthesis of multivinyl compounds that would not

homopolymerize upon addition of organolithium reagents. These constraints explain why the

only initiator of precise functionality (higher than 2) ever synthesized by this method is the

tricarbanionic compound of Quirk and Tsai20 who obtained it upon addition of sec-butyllithium

onto a molecule containing three 1,1 -diphenylethylene-type unsaturations (Figure 1-2).














R-Li + R'-X R-R' + LiX



X : Halide atom

R and R' : Alkyl groups



Figure 1-1. Wurtz coupling reaction.







3 sec-BuLi~ezn( \ e













Figure 1-2. Synthesis of a tricarbanionic initiator.


s-BuB SI
s-Bu. I s u -B


I


s Bu
s-BUSl


"Sl,


-SI-
'U

g,
s,


8 sec-BuL1 3
THF


SI


SISI


Figure 1-3. Synthesis of polylithiated carbosilane dendrimers.












E~ Li 0 L
Li O Li
Li


Figure 1-4. Synthesis of pluricarbanionic species from DVB.



~C~Br + RLi OLi + R-Br



Figure 1-5. Halogen-lithium exchange reaction.




2 s-BuLi
Br Br ~THF LI \/ L





Figure 1-6. Synthesis of a dicarbanionic initiator from a dibromo precursor.


s-BuLi +









CHAPTER 2
A NOVEL ADDITIVE-FREE DICARBANIONIC INITIATOR FOR THE SYNTHESIS OF
POLY(STYRENE-b-DIENE-b-STYRENE) TRIBLOCK COPOLYMERS IN NON-POLAR
MEDIUM

2.1 Introduction

Living anionic polymerization is certainly the most reliable and versatile technique for

the synthesis of block copolymers.47,48 Under appropriate conditions anionic polymerization

indeed proceeds in absence of transfer and termination reactions for a large number of

monomers. For this reason, it occupies a key position in the industrial production of block

copolymers, the most emblematic being SBS triblock copolymers comprising a low Tg

polybutadiene block flanked by two glassy polystyrene end blocks. Such triblocks are

industrially obtained by sequential polymerization of styrene and butadiene initiated by

butyllithium (BuLi), followed by the deactivation of growing living carbanionic chains by a

difunctional electrophilic reagent.49-5 Although applied for the last forty years this method is

very sensitive to the stoichiometry of the final dichain coupling, and therefore fails to deliver

diblock-free pure triblock copolymers. The presence of diblock contaminants in the final

sample is detrimental to excellent stress-strain properties--23% decrease in tensile strength

due just 5% of diblocks--and prejudicial to its ultimate in commercial applications.52 The use

of a dicarbanionic initiator that could trigger polymerization in two directions and afford SBS

triblocks by a two-step sequential monomer addition therefore appeared as the only viable

alternative.15,53 However, one maj or difficulty met in the latter case is the limited solubility of

dicarbanionic initiators in apolar solvents, media that are required for the preparation of a

polybutadiene (PB) central block with a high content in 1,4-PB units and elastomers with

optimal properties (high tensile strength and elongation at break). Although a number of

patents and papers have reported on the synthesis of various organolithium diinitiators in non-

polar solvents, none of them could be practically used to prepare well-defined SBS triblock

copolymers with a large content in 1,4 linkages and equal amounts of cis- and trans-









unsaturations. Whether obtained by reaction of BuLi with appropriate diolefinic species in 2: 1

ratio (m-diisopropenylbenzene, 16,54-72 double diphenylethylene-type moleculesl7,18,73-82 O

more complicated precursorsl9,83,84) Or by generation of ion-radical species which then couple

(electron-transfer from lithium to co-substituted vinyl monomers),52,85-103 all these

organolithium diinitiators indeed require the presence of active polar additives--often in

small proportions--to efficiently initiate polymerization, modifying the stereochemistry of the

polydiene block and increasing its content in 1,2 unsaturations. A dicarbanionic initiator that

would be entirely soluble in apolar medium in absence of any additives or ligands and yet

reactive enough is thus still in great demand.

2.2 Literature Overview on Symmetric ABA Triblock Copolymers

Linear triblock copolymers consisting of two chemically different monomers of the

symmetric type contain three blocks of A and B monomers arranged in a way that the first

and the third block have the same chemical nature and molecular weight, whereas the middle

block differs in chemical nature. There are three possible procedures to synthesize block

copolymers of this type.

2.2.1 Sequential Monomer Addition

The preparation of block copolymers by sequential addition of monomers using living

anionic polymerization and a monofunctional initiator is the most direct method for preparing

well-defined block copolymers. In this reaction scheme (Figure 2-1), the first monomer is

polymerized by an alkyllithium initiator followed by the polymerization of the second one.

After complete consumption of the second monomer, an equal amount of the first monomer is

added to the reaction mixture resulting in an ABA triblock copolymer (Figure 2-1).

This approach involves three monomer additions, and, therefore, the probability of

partial termination of growing chains during the second or the third reaction step increases,

due to impurities present in the monomers used. This can result in the presence of undesirable









homopolymer A and/or diblock AB in the final product. Furthermore, small differences in the

quantity of monomer A used in the first and third step may result in the synthesis of a

triblock, which is not perfectly symmetric. Another point that must be considered is the ability

of monomer B to initiate polymerization of monomer A. If this criterion is not fulfilled, ill-

defined products will be obtained. This critical aspect can be illustrated by considering the

preparation of SBS triblock copolymers. Indeed, the rate of the crossover reaction of

polybutadienyllithium to styrene monomer to form polystyryllithium chain end is slow

compared to the rate of styrene propagation (order of reaction rate constants is

kSB>kss>kBB>kBS).104 Because of the slow rate of styrene initiation relative to propagation, a

broad molecular weight distribution would be expected for the final polystyrene block

segments. To obtain polystyrene end blocks with narrow molecular weight distributions, a

Lewis base such as an ether or amine is often added before styrene monomer addition in this

third stage of the triblock copolymer synthesiS. 50,53,105-108 Sometimes even monomer A may

not be able to initiate polymerization of monomer B appropriately. A typical example is the

preparation of PI-PS-PI triblock copolymerS.109 Initiation of styrene by PILi can be successful

if a small amount of THF is used before the addition of styrene,109 but one should have in

mind that the presence of THF will alter the microstructure of the third PI block. It is obvious

that the outlined method cannot be used in the present example if high 1,4-microstructure of

the PI blocks is desired. However, it can be applied in the case where the 1,4-microstructure is

not essential. In this case THF can be added from the beginning of the polymerization and

both end PI blocks will have the same microstructure.

2.2.2 Coupling of Living AB Chains

Another general method for the of ABA triblock copolymers involves first the

synthesis by a two-step sequential monomer addition sequence of a living AB diblock

copolymer, having the same composition but half the molecular weight of the final triblock









copolymer. Then an appropriate coupling agent, i.e. a compound having two functional

groups able to react with the active anions forming covalent bonds, is used to connect two AB

chains producing the desired symmetric triblock copolymer (Figure 2-2).49-51 This two-step

method with coupling offers many advantages over the three-step sequential monomer

addition method. From a practical point of view, the polymerization time is reduced to one-

half that required for the three-step synthesis of a triblock copolymer with the same molecular

weight and composition.110 One problem avoided in the two-step process is that the Einal

crossover step from polybutadienyllithium or polyisoprenyllithium to styrene is eliminated.

The elimination of the third monomer addition step also decreases the possibility of

termination by impurities in a third monomer addition. However, caution should be exercised

in the stoichiometry of the coupling reaction. In practice, it is difficult to control the

stoichiometry of the coupling reaction and many two-step syntheses yield triblock copolymers

with significant amounts of uncoupled diblock contaminants.110-112 Indeed, excess of living

anions is usually used to ensure complete reaction of both groups of the coupling agent. In

general, the presence of diblock material affects the triblock copolymer morphology,112 which

has a detrimental effect on physical properties of triblock copolymers (ultimate tensile

strength and elongation at break).'0mlio This makes necessary an additional fractionation step

in order to separate the ABA triblock copolymers from excess AB diblock copolymers.

Finally, the coupling reaction may be completed in days. Obviously, this synthetic route is

more time consuming than the sequential addition method.

PS-PI (or PB)-PS triblock copolymers have been synthesized by the coupling method

by Morton and co-workers (Scheme 2-2).53 A PS-PD diblock is formed first where the length

of the polydiene (PI or PB) block is half of that in the Einal triblock copolymer. Then the

living diblocks are coupled using (CH3)2SiCl2 aS the coupling agent. A small excess of the

living diblock is used in order to ensure complete coupling. Solvent/nonsolvent fractionation









of the crude product is performed in order to isolate the pure triblock copolymers. These

triblocks have found applications as thermoplastic elastomers in everyday life. PD-PS-PD

symmetric triblock copolymers can also be made in the same way. (CH3)2SiCl2 Can alSo be

used as a coupling agent for PS (or PD)-polysiloxane living diblocks in order to produce

triblocks with a siloxane central block.113,114 When the outer blocks are PB with high 1,4-

microstructure, PE-PDMS-PE triblocks with semicrystalline outer and elastomeric inner

blocks are obtained by hydrogenation of the parent PB-PDMS-PB materials.11

Another advantage of the two-step process is that it is more versatile with respect to

the chemical composition of the center block. With the two-step method, the center block can

be a more reactive monomer that would not be capable of reinitiating polymerization of

styrene because of the increased stability of the chain end (Figure 2-3).

For example, bis(bromomethyl)benzene has been used as a coupling agent in cases

where living (meth)acrylate (M) and vinylpyridine (2VP) anions were involved." Due to the

greater reactivity of the C-Br bond, this agent is efficient for coupling less reactive anions at

lower temperatures (Figure 2-3). Well-defined symmetric triblock copolymers with pyridine

or (meth)acrylate central blocks can be prepared in both cases. Varshney et at 116 USed

terephthaloyl chloride as the coupling agent for the synthesis of ABA symmetric triblock

copolymers with PS, P2VP, or polydiene of high 1,4 microstructure end blocks, and poly(tert-

butyl acrylate) middle blocks. The PtBuA blocks could be converted to other types of acrylic

blocks by transesterification reactions, leading to a larger variety of ABA triblock

copolymers .

2.2.3 Use of a Difunctional Initiator

One of the most versatile methods for the synthesis of symmetric ABA triblock

copolymers is the use of a difunctional initiator, i.e., an organometallic compound having two

anionic sites able to initiate polymerization, in a two-step sequential monomer addition









sequence. The middle B block is formed first followed by the polymerization of A monomer.

A number of difunctional initiators soluble in polar and/or nonpolar solvents have been

reported in the literature.15-19 The points that deserve attention are:

i) The quality of the difunctional initiator used, which is essentially its ability

to form pure difunctional polymer. This depends on the precise chemical structure of the

initiator and sometimes the solvent medium as well as the chemical nature of the monomer

used. Not all known difunctional initiators behave in the desired manner in all solvents

commonly used for anionic polymerization and towards any available monomer. If the

initiator/solvent/monomer system cannot generate pure difunctional polymers, it is obvious

that the final product will be a mixture of homopolymer, diblock, and triblock copolymer.

ii) The purity of the monomers must be high in order to avoid deactivation of one or

both initiators' active sites or lead to premature termination of growing chains, which will

result in a mixture containing the desired triblock and other undesired impurities that are

difficult to be eliminated by fractionation or other separation methods.

In our case, we will be especially interested in the hydrocarbon-soluble dilithium

initiators required for the two-step synthesi s of poly styrene-b-polybutadi ene-b-poly styrene

triblock copolymers. Indeed, a hydrocarbon-soluble dilithium initiator ensures that the

polydiene center block will have a high 1,4-microstructure and a correspondingly low glass

transition temperature.

2.2.3.1 Divinylbenzene derivatives

Adduct of divinylbenzene (DVB) derivatives with s-BuLi were the first examples of

difunctional initiators studied since the early 1970's.54,58,59 Different studies on DVB

demonstrated first that the two unsaturations of the meta isomeric compound were equally

reactive to BuLi, in opposition to the conjugated unsaturations of the para compound (1,4-

DVB). However, a mixture of soluble mono- and dilithiated and oligomeric species, with









functionality higher than two due to possible polymerization of DVB, was obtained which did

not guarantee a good control of the diene polymerization. Another dilithium initiator claimed

by Rempp and colleagueS59,61 was a bis-adduct of BuLi onto m-Diisopropenylbenzene (m-

DIB), which was an efficient bifunctional initiator in apolar solvent that affords a good

control over the molar mass and narrow molar mass distribution even in the presence of a

mixture of multiadduct, diadduct and unreacted sec-BuLi. Foss et al""8 and Cameron et al.60

have also used m-DIB as a difunctional precursor, but had to add a o-complexing polar agent

such as triethylamine (Et3N) to avoid precipitation of the initiator. However, even in the

presence of Et3N a mixture of species was still observed after the reaction between m-DIB and

sec-BuLi. We have to wait the work of Yu et al.,64-66 who also revisited these experiments and

demonstrated that the use of precursors such as 1,3 -diisopropenylbenzene with twice the

amount of sec-BuLi in non-polar medium such as cyclohexane did not result in a soluble

well-defined truly bifunctional initiator; they found that the reaction of tert-BuLi--instead of

sec-BuLi--and 1,3-DIB in the presence of 1 equivalent of Et3N at -20 oC can lead to a well-

defined difunctional initiator, i.e. 1 ,3 -bi s(1 -lithi o- 1,3 ,3 '-trimethylbutyl)b enzene (DiLi)

(Figure 2-4).

Some other o-complexing polar agents such as diethyl ether, tert-butyl methyl ether,

N,N,N',N' -tetramethyl ethyl enedi ami ne (TMEDA) and THF were found to b e effi ci ent pol ar

additives, but leading to a high 1,2-microstructure of the PB block.68 The same group finally

demonstrated that the combination of the initiator seeding technique and weakly polar

additives such as tert-BuOLi and anisole was necessary to prevent the presence of residual

initiator and achieve equal reactivity of both ends active centers so as to obtain SBS and

MBM triblock copolymers with high content of 1,4-PB units.68 7T-COmplexing agents such as

1,2,4,5 -tetramethylbenzene (durene) or tetraphenylethylene (TPhE) were also proposed which









did not interact so strongly as o-complexing agents with the Li+ cation to bring about the

dissociation of the organolithium aggregates.69,70,72

2.2.3.2 Diphenylethylene-type molecules

Other researchers concentrated their efforts on the reaction of double

Diphenylethylene-type (DDPE) molecules with stoichiometric amount of sec-BuLi in non-

polar solvents. Broske et al.76,78 Observed at 600C after 2 hours in cyclohexane in presence of

a small excess of sec-BuLi the formation of a soluble well-defined difunctional initiator with

a negligible quantity of oligomers. It was demonstrated that this difunctional initiator was

efficient in the case of the butadiene polymerization, but only at low monomer conversion.

Later, Quirk and Ma79 TepOrted that the dilithium initiator based on 1,3-di(1-

phenylethenyl)benzene (PEB), although soluble in hydrocarbon solvents such as cyclohexane

and benzene, led to bimodal molar mass distribution for molar masses lower than 50,000 and

150,000 g.mol-l in the cases of PS and PB, respectively. This is only after the addition of sec-

butoxylithium (sec-BuOLi) as an additive that PB samples were obtained with a narrow molar

mass distribution and a high content of 1,4-PB units (Figure 2-5).79

More recently, Tung and LO,17,18,80-82 who first proposed the idea of using DDPE as

precursors, developed dilithium initiators based on different derivatives of DDPE (Figure 2-

6), which were soluble in benzene, cyclohexane and/or toluene depending on the structure of

the DDPE derivative. Although the addition reactions of these latter precursors with sec-BuLi

were found to be clean and rapid, the resulting dilithium initiators were insoluble forming fine

suspensions, which would coagulate into hard particles after several hours. The fine

suspensions were effective in initiating butadiene or isoprene polymerization, but only after

solubilizing the dilithium initiators by using additives such as N,N,N' ,N",N"-

pentamethyldiethylenetriamine (PMDETA) and lithium alkoxides or by reaction with a









fractional amount of diene first and then with the rest of the monomer, also called seeding

technique.

Finally, more complicated precursors such as a,co-bis(phenylvinylidenyl)alkaneS19,83,84

and a,co-bis(isopropenylphenyl)alkaneS19,83,84 Of Some other listed below (Figure 2-6) were

developed and found to be effective for the polymerization of styrene or diene, but difficult to

synthesize.

2.2.3.3 Use of alkali metals

Another way of making diinitiators consists in the reaction of alkali metals with a-

substituted vinyl monomers.88,89,91-101 For example, this reaction is useful for the preparation

of homogeneous difunctional initiators from a-methylstyrene in polar solvents such as THF.

Because of the low ceiling temperature of a-methylstyrene, dimers or tetramers can be

formed depending on the alkali metal system, temperature, and concentration. SBS triblock

copolymers were synthesized using a dicarbanionic initiator formed by the reaction of lithium

metal and a-methylstyrene (Figure 2-7).89 However, the presence of THF needed for the

formation of the dicarbanionic initiator resulted in SBS triblock copolymers with poor

mechanical properties.

Many aromatic hydrocarbons such as naphtalene can also react with alkali metals by

reversible electron transfer in polar aprotic solvents such as THF to form stable solutions of

the corresponding radical anions (Figure 2-8).47,48,102,103 PEO-PI-PEO symmetric triblock

copolymers were synthesized using sodium or potassium naphthalene as the difunctional

initiator.10 ISoprene was polymerized first followed by addition of EO (Scheme 2-8). The

copolymers had a variety of block compositions and total molecular weights. Their molecular

weight distributions were narrow and monomodal. Since Na or K naphthalenide is soluble

only in polar solvents (e.g., THF), the microstructure of PI obtained was mostly 3,4. Thus,

these initiators are of limited utility for the preparation of elastomeric block copolymers









because they are prepared and utilized in polar solvents such as THF that result in polydiene

with high vinyl microstructures and relatively high Tg values.

2.3 Results and Discussion

We reported in chapter 3 the preparation of tri- and tetrafunctional polylithium organic

compounds by lithium-halogen exchange and their use as initiators for the synthesis of

polystyrene (PS) and polybutadiene star polymers and SBM triblock star copolymers (Chapter

3).121 This method rests on the metallation of poly(arylhalide)s whose halogens are carried by

separate aryl rings. However, the polylithiated species formed are soluble only in the presence

of o/C1-coordinating ligands. We propose here a new dicarbanionic initiator that is totally

soluble in apolar media in absence of any additive, and is efficient enough to generate well-

defined telechelic PB and SB S triblock copolymers with a high content in 1,4-PB units.122,123

For this purpose, 3-pentadecyl phenol, obtained from cashew nut shell,124,125-

renewable resource material and by-product of agro industry--served as a precursor for the

dibromo compound viz, 1-bromo-4-(4' -bromophenoxy)-2-pentadecyl benzenel26 (I); the latter

was subsequently dilithiated and eventually used for difunctional initiation. In this chemistry

advantage is taken of the saturated 15-carbon side chain to obtain a soluble dilithiated

initiator.

The dibromo compound I was synthesized by a two-step synthetic procedure (Figure

2-9). In the first step, 1 -pentadecyl-3-phenoxy benzene was prepared by reaction of potassium

3-pentadecyl phenolate (product of the deprotonation of 3-pentadecyl phenol) and

bromobenzene. In the second ste the dibromo recursor 1 was obtained in excellent yields

(84 %) after bromination in para position of 1 -pentadecyl-3-phenoxy benzene (Figure 2-9).

The structure of the dibromo compound (I) was confirmed by 1H and 13C MR Spectroscopy

and mass spectrometry (Figures 2-10 and 2-11).









Next, 1 was treated with stoichiometric amounts of sec-but llithium (s-BuLi) in

cyclohexane to generate 1' and 2-bromobutane (Figure 2-12). Among the different

alkyllithium reagents sec-butyllithium was found to be the most efficient for the

bromide/lithium exchange reaction (quantitative reaction with no side reactions such as

coupling and elimination).36 tert-Butylithium is more suitable for the iodine/lithium exchange

reaction.42 To avoid any chance of deactivation of the growing carbanionic chains of PS or PB

by 2-bromobutane during polymerization (Figure 2-13), another equivalent of s-BuLi was

added prior to monomer addition to give 3,4-dimethylhexane (2) as previously demonstrated

(Figure 2-12).121,127,128

Indeed, the different possible secondary reactions that could happen during the

halogen-lithium exchange reaction were previously studied.127,128 It was first demonstrated by

gas chromatography analysis that aryllithium species are not nucleophilic enough to react

with 2-bromobutane without the presence of polar additives such as

tetramethylethylenediamine (TMEDA). Even in presence of TMEDA, this reaction is slow

since only 10 % of 2-bromobutane is consumed after 90 minutes of reaction (Figure 2-13).

Some other previous studies have also shown that benzene when used as solvent can react

with s-BuLi in presence of TMEDA to give the corresponding phenyllithium species (Figure

2-13).129,130 The latter are able to initiate the monomer polymerization to generate a

multimodal distribution.131

The diadduct product 1' resulting from the reaction of 1 with s-BuLi took in

cyclohexane a yellow color at the concentration of [Li ] = 5.3x10-2 M and a gelly aspect

unlike the insoluble precipitate formed from the reaction of 4,4'-dibromobenzene with s-BuLi

in the same solvent.121 The formation of such a physical gel instead of a solid precipitate is

due to the presence of the C15 side alkyl tail which helped preventing the irreversible

precipitation of the dilithiated species.









The halogen/lithium exchange reaction between I and s-BuLi was thoroughly

investigated by 1H and 13C NMR spectroscopy and mass spectrometry (Figure 2-14).The

structure of the dilithium diadduct I' was first confirmed by H ( ood inte ration values) and

13C NMR spectroscopy analysis of the product isolated after methanol quenching of a solution

of I' in cyclohexane ([Li ] = 5.3x10-2 M). Moreover, mass spectrometry analysis showed the

total disappearance of the peak of the dibromo precursor I (M = 538 g/mol) in favor of 1'

with a principal peak at M = 381 g/mol after methanolysis (Figure 2-15).

After checking the quantitative halogen/lithium exchange reaction at this

concentration ([Li ] = 5.3*10-2 M) and the truly difunctional initiator structure, styrene or

butadiene were polymerized by addition of the corresponding monomer (Figure 2-16). After

introduction of a few monomer units the dilithiated species appear totally soluble in

cyclohexane even in absence of stirring and of any polar additives. On deactivation of the

living carbanionic chains by ethylene oxide after complete monomer consumption a,co-

dihydroxy telechelic polymers were obtained from 1'. Analysis by size exclusion

chromatography (SEC) indicated the complete consumption of the initiator (Figure 2-17). No

peak attributable to residual I could be detected in the low molar mass region, and the only

trace seen was a narrow and monomodal peak corresponding to the expected linear polymer

in the high molar mass region (Figure 2-17).

Such good control over the molar mass (good agreement between the experimental

and theoretical values of molar masses) and narrow molar mass distribution (M, /Mir <1.1)

reflects a rate of initiation by I' comparable to that of propagation (Table 2-1). The structure

of the difunctional polymer formed could be established first by 1H NMR analysis using a,co-

dihydroxy telechelic polybutadiene samples of low degrees of polymerization (Figure 2-18).

From the ratio of the integration values due to the signal of the aromatic protons of the

difunctional initiator (3= 6.5-7.5 ppm) to that of -CH2-OH chain ends (3= 3.7 ppm) the









actual functionality of the samples prepared could be determined: functionality values close to

2 were obtained for the polybutadiene telechelics. Furthermore, the microstructure of the

polybutadiene samples determined by 1H and 13C NMR spectroscopy (Figures 2-18 and 2-19)

demonstrated a high percentage of 1,4-PB units (86-91%) in agreement with the fact that the

polymerization occurred in an apolar solvent without any additives. This proportion of 1,4-PB

units was almost half constituted of 1,4-cis and 1,4-trans (Table 2-1 and Figure 2-19), which

is generally the case for linear polybutadiene synthesized using butyllithium as initiator in

apolar solvents."

After demonstrating the efficiency of this dicarbanionic initiator for the synthesis of

polybutadiene telechelics with optimal elastomeric properties (high percentage of 1,4-PB

units), SBS triblock copolymers were derived by sequential anionic polymerization of

butadiene (B), and styrene (S) with 1' as initiator (Figure 2-20).

The initiation of styrene by polybutadienyllithium being slow compared to the reverse

situation, it was necessary to dilute further the reaction medium with fresh cyclohexane and

some THF (Cyclohexane/THF: 100/1 in volume). Upon introduction of styrene, the color of

the medium changed instantaneously from the character sti c yellow color of

polybutadienyllithium carbanions to the orange color of polystyryllithium carbanions. By

taking an aliquot before the introduction of styrene, the formation of the SBS samples could

be easily followed by SEC (Figure 2-21).

The absolute molar masses of the SBS triblock copolymers were deduced by 1H NMR

spectroscopy knowing that of their polybutadiene precursor determined by SEC (Table 2-2

and Figure 2-22). In all cases narrow molar mass distributions were observed either for the

polybutadiene precursor or for the triblock copolymer structure with a complete consumption

of the polybutadiene precursor during the polymerization of styrene as attested by SEC with

the disappearance of the polybutadiene peak (Figure 2-21): this demonstrates that the growth









of either the polybutadiene middle block or the two polystyrene glassy end blocks occurred

under living conditions. The mechanical properties, e.g., ultimate tensile strength and

elongation at break, of the SBS triblock copolymers containing small polystyrene end blocks

(%wt (PS) < 35%) were also studied to bring an other proof of the well-defined structure of

these SBS triblock samples. As shown in Table 2-2, excellent mechanical properties are

obtained with ultimate tensile strength higher than 30 MPa and elongation at break of 1000%

(Runs 10 and 11, Table 2-2) which are in good agreement with the mechanical properties

generally obtained by SBS copolymers.132-135

2.4 Conclusion

In summary, the halogen-lithium exchange reaction has been successfully applied to

generate a new dicarbanionic initiator from a dibromoaryl compound. The presence of a C15

side alkyl tail in the dibromo precursor is essential to the solubility of the dilithiated initiator

in apolar solvent. This is the first example of dilithiated species initiating efficiently anionic

polymerization in absence of additive and affording well-defined polybutadiene telechelics

with a high percentage of 1,4-PB units (91%).122,123 This initiator has proved to be very

efficient in providing SBS triblock copolymers with excellent mechanical properties, e.g.,

ultimate tensile strength higher than 30 MPa and elongation at break of 1000%.122,123 A long-

standing problem faced by the industry of styrenic thermoplastic elastomers for the last forty

years could be worked out with the results disclosed in this contribution.










Hydrocarbon
C4Hi +solvent C4H9 tCH2-CH CH2-CHO Li



PSLi


SPS -CH2-CH=CH-CH2 CH2--CH--CH2--CHO Li
Hydrocarbon m-1
solvent
PS-b-PBLi




Hydrocarbon nSCBCZ-HC H-1~ ~
solvent
(Lewis base) i


PS-b-PB-b-PSLi


PS-b-PB-b-PSLi + CH30H >P--BbP


Figure 2-1. Synthesis of SBS tribock copolymer by sequential monomer addition.


Benen aPS LiO ) PS-b-PeLiO


(C~)2i~2 PS-b-PI-b-PI-b-PS + PS-b-PI Li 1 OO PS-b-PI-b-PS
(Li:Cl = 1.2:1) 2. Fractionation


e( xcess)


(pure triblock)


Figure 2-2. Synthesis of SIS triblock copolymer by coupling of living chains on
di chlorodim ethyl silane.


s-Bu'i +













THF PSL
-78 OC


OC(CH3)3


1.
PS-b-PtBAe Li >
2. CHOH


PS-b-PtBA-b-PS


Figure 2-3. Synthesis of P(S-b-tBA-b-S) triblock copolymer by coupling of living chains on
bis(bromomethyl)benzene.


Cyclohexane/Et3N
+ 2 t-BuLi
-20 OC


Li0 PB Li0 1. PS-b-PB-b-PS
Cyclohexane / 25 OC 2. CHzOH




Figure 2-4. Synthesis of SBS triblock copolymer using 1,3-diisopropenylbenzene as
precursor.


Benzene


2 s-BuLi +


/> LiO PB Lie
Benzene / s-BuOLi


-> PS-b-PB-b-PS


1. Bezee /TH

2. CH30H


Figure 2-5. Synthesis of SB S triblock copolymer using 1,3-di(1 -phenylethenyl)benzene as
precursor.




















D


CH3' CH3


H


H3, CH3


N


Figure 2-6. Complex diolefinic precursors used for the synthesis of organolithium diinitiators
(19,83, 16, 84, 117, E-M17,82,118, 119, 120~



















CH3 CH3 CH3 CH3 CH3
2 H2 6 .tO~ + Li C--CH2-- H2C-C C--CH2-H2C- Li





CH3 CH3 CH3 CH3
O O C-CH2-C-CH2-H2C-C- H2c t

Lii Li~Li





(Li+ "R- Li ) a PS-b-PB-b-PS





Figure 2-7. Synthesis of SBS triblock copolymer from a dicarbanionic initiator formed by the
reaction of lithium metal and co-methylstyrene.






+ K K THI7" KO OPIO K





O KO PEO-b-PI-b-PEOO K C `O PEO-b-PI-b-PEO
400C B



Figure 2-8. Synthesis of P(EO-b-I-b-EO) triblock copolymer from a difunctional initiator
formed by the reaction of potassium metal and naphtalene.










Cu Powder
Br K yield 57% O


CisH31 C15H31

Br2
yield = 84%






1 C15H31


Figure 2-9. Synthesis of 1-bromo-4-(4' -bromophenoxy)-2-pentadecyl benzene Q).







































7r.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.6 1.0 0.5


eg fd


t~ 1 CH, CHgk~H, g


15 156 15 152 150 14 146 14 142 140 13 136 13 132 130 128 126 12 122 120 118 116 114 112

4- 6t(ppm)



Figure 2-10. 1H and 13C NMR spectra (CD2 12, 400 MHz) of 1-bromo-4-(4' -bromophenoxy)-
2-pentadecyl benzene (1).


abba




H H H CH, CH, CHi,
a b c d e 13


CHCl


I


I I I_































miz (glmol)



Figure 2-11. Mass spectrum of 1-bromo-4-(4' -bromophenoxy)-2-pentadecyl benzene (I).


Urr-CUY~YULC-YY-Y L~I- --LI~LWCCI -~VLIILI-





11 C, ,H z


5,9E5

~a.'jg~

1.Pr5

_1.2~5

5.9L4

n.nFn


425


380
A h~,


Br O Br Cycslo~he ne L O 8 O i

1 CisH31 R.T., 30 min 1' C15H31


+1 2

2


Figure 2-12. Synthesis of a dicarbanionic initiator by halogen-lithium exchange reaction using
1_as dibromo precursor.


213 PW













I ""Li








~O -LI


Deactivation ofthe
carbanionic sites



Li0~t Li,
Insoluble


Br


TMEDA


H Li
TMEDA


Solvent Metalation


Deactivation of the PS L >
hiving chain ends T MEDA
Benzene


+ LiBr


Figure 2-13. Secondary reactions resulting from the halogen-lithium exchange reaction.















a d f '13


7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.0]5 7.00 6.95 6.90 6.85 6.80 6.75


6.60 6.55


di he


CH, CH, 13CHz


158 156 164 152 150 148 146 144 142 140 138 136 134 132 130 128 126 124 122 120 118 116 114 112
(pp m)



Figure 2-14. 1H and 13C NMR spectra (CD2 12, 400 MHz) of the addition product of I with
sec-butyllithium obtained after methanolysis.












Cl SH,,


Figure 2-15. Mass spectrum of the addition product of 1 with sec-butyllithium obtained after
methanolysis.




Br OBr C~ycslo~hue ne Li Li+2
1 CisH31 R.T., 30 min 1'C15H31 2


1) ,, R.T., 24h


o CisH31
3) CH30H/HCI


Figure 2-16. Synthesis of ot,o -dihydroxy telechelic polybutadiene from 1'.


mlz (glmol)






















11


lI
lI


25 2r8 30 32 3r4 36~ 38~ 40 42 44~ 4r6 48 50


I I
SI





'''' '''' ''' '''' ''' ''I
26 2 30 2 3436 8 4042 4 46 8I 5
Elutin tim (mi1

Figre2-7.SE elogam o (S)2diuntina poysyrnean (P)2diuntIIa







Figure 2-17. n S C ) eluogram pof(PS)2difn(unctionable poytyee n PB2diuctoa












"d C~,H,,





















7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
-~ 6/ (pp m)


Figure 2-18. 1H NMR spectrum (CD2 12, 400 MHz) of a,co-dihydroxy terminated
polybutadiene (Run 3, Table 2-1).




CHCH=CHCH CH=CH C, ,
1 45

5, 6


CH C1,

2, 3










140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20
r- a (ppm)


Figure 2-19. 13C NMR spectrum (CDCl3, 400 MHz) of a a,co-dihydroxy terminated
polybutadiene (Run 6, Table 2-1).
















Br~~~0 O r Cysohe e L Li + 2


C is1H31 R.T., 30 min 1' C15H31


PB (SLi )


~~ P B-b-S LiO 2
Cyclohexane/THF (100/1)
R.T., 12h


Cyclohexane, R.T., 24h


CH 0HH










Figure 2-20. Synthesis of SBS triblock copolymer from 1'.


I
I
PB,
r
I
I
I
I
r
I
r
I
I
r
'L
'1
i


22 24 26 28 30 32 34 36 38 40 42

Elution time I min -






Figure 2-21. SEC eluograms monitoring the formation of a SBS triblock copolymer initiated

in cyclohexane with 1' (Run 11, Table 2-2).


























a and d


7.5 7.0 6.5


4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
S/ (ppm)


MHz) of a SBS triblock copolymer (Run 11,


Figure 2-22. 1H NMR spectrum (CDCl3, 400
Table 2-2).


Table 2-1. Characterization of PS and PB samples synthesized from 1' difunctional initiator.["]


Microstructure (%)[d]

1,4-cis 1,4-trans 1,2


Sample
no.

1

2

3

4

5

6

7

8


Yield


Polymer My My M,


Mn (theo)1


12000

44000

2000

7000

17000

43000

52000

70000


PS2

PS2

PB2

PB2

PB2

PB2

PB2

PB2


11400

43800

2100

6200

16600

43700

51900

67400


1.15

1.13

1.2

1.13

1.07

1.06

1.08

1.1


[a] Butadiene polymerization was initiated in cyclohexane with 1' ([Li ] = 5.3*10-2 M). [b]
Determined by SEC in THF using a refractometric detector. A conversion factor of 0.55 was
used for the calculation of the PB molar mass. [c] My (theo) = Mbutadiene X ([Butadiene]/[-PhLi]i)
x 2. [d] Calculated by 1H and 13C NMR.


6.0 5.5 5.0 4.5
r-














Table 2-2. Mechanical properties of SBS triblock copolymers initiated by II.1ai


Ultimate tensile Eogto
at break
strength (MPa)
(%)


PB2
Sample
no.
Mn [b] My /Mn [b] Mn [b]
9 6200 1.13 20400


SBS



18300 1.2


1,4-PB "
(%)


10 43700
11 67400


78300 60300
110900 93500


29.5
33.8


900
1000


[a] Butadiene polymerization was initiated in cyclohexane with 1' ([Li ] = 5.3*10-2 M). [b] Determined by SEC in THF using a refractometric
detector. A conversion factor of 0.55 was used for the calculation of the PB molar mass. [c] Determined by 1H NMR from the molar mass of the
polybutadiene block, assuming 100% efficiency in the initiation of the second block.









CHAPTER 3
TRI- AND TETRACARBANIONIC INITIATORS BY A LITHIUM/HALIDE EXCHANGE
REACTION: APPLICATION TO STAR-POLYMER SYNTHESIS

3.1 Introduction

Star-branched polymers represent the most simple polymer branched structures. A

star-branched polymer consists of several linear chains linked together at one end of each

chain by a single branch or junction point,136-138 in Opposition to graft, dendrimer-like, and

hyperbranched polymers. Among these star-branched polymers, three categories of star

polymers can be distinguished by the nature and the lengths of their branches:

Asymmetric stars with branches of same nature (i.e., same polymer), but

different length.139,140

"Mikto-arm" stars which are constituted of polymer branches of different nature

connected to the same core.139

(A)n (homopolymer) or (AB)n (diblock branches) stars connecting branches of

same nature and length.140,141

We will be especially interested in this chapter by the (A)n and (AB)n star polymers.

Star polymers are produced through three general synthetic routes (Figure 3-1).141 The

first also called "arm-first" method involves the synthesis of preformed arms followed by

reaction with a multifunctional linking agent. The second route is a slight variation of the

latter one, which sometimes is also termed the "in-out" method. This approach entails a

coupling reaction of linear living chains with multifunctional agent such as divinyl

compounds and a cross-over reaction to a second monomer to form star polymers. The third

one is the "core-first" technique, which involves the use of a multifunctional initiator to

initiate the polymerization of multiple branches of the star. Basically, the number of arms of

the star polymer can be determined by the number of initiating sites. The latter approach is a

major challenge since it requires the prior design of well-defined multifunctional initiator.









Furthermore, all the initiation sites must exhibit the same reactivity. However, anionic

polymerization suffers from the lack of pluricarbanionic initiator exhibiting precise

functionality and good solubility. In comparison to controlled radicall42 and cationiC143

polymerizations where various plurifunctional initiators were described, only a few

pluricarbanionic initiators could be successfully developed in anionic polymerization.20,22

3.2 Literature Overview on (A)n and (AB)n Star Polymer Synthesis

3.2.1 "Arm-first" Method

Two distinct strategies were used in this case. The first strategy involves the synthesis

of living macroanionic chains and their subsequent reaction with a well-defined

multifunctional electrophile, which acts as the linking agent (Figure 3-2).

In such a case, the polymer chains possess either active centers (*) at their chain ends

or functions capable of reacting with the antagonist functions (F) of the coupling agent. The

required conditions for obtaining well-defined star polymers (i.e. low molecular weight

distribution) are the precise functionality (number of functions F) of the coupling agent and

the selectivity of the reaction between active centers and the latter F functions.

In some other cases, it was needed to compensate for the lack of deactivating linking

agent of precise and higher functionality by the copolymerization of the living macroanionic

chains with a difunctional comonomer (divinyl, diepoxide, etc...). This second strategy was

elaborated to access star polymers with a very high number of branches. The principle of the

copolymerization of living chains with a difunctional comonomer is illustrated in Figure 3-3.

The grafting reactions on the pendant vinylic groups--which can be in competition

with the intramolecular cyclization--has as a consequence on the formation of a cross-linked

core possessing a certain number of branches and affording by the fact a star structure.

However, it is difficult to avoid the presence of residual linear chains because of the low

reactivity of the pendant sites (double bonds) towards active centers.









3.2.1.1 Use of multifunctional coupling agent

Several linking agents have been used for the synthesis of star polymers." The most

important of those are chlorosilaneS144 and chloromethyl or bromomethyl benzene

derivatives. 145, 146

Chlorosilane compounds. The use of tetrachlorosilane as electrophilic coupling agent

for the syntesis of four-armed PS stars was described for the first time in 1962 by Morton et

all144 ISomolecular polystyryllithium chains initiated by n-butyllithium were added on this

tetrafunctional linking agent in hydrocarbon solvent. However, this reaction is not complete

even in the presence of large excess of living chains. The purification by a fractionation

technique was needed in this case to separate the four-arm from the three-arm stars.

In 1965, Zelinski and Woffordl47 also used the tri- and tetrachlorosilane derivatives for

the synthesis of PB star polymers by deactivation of polybutadienyllithium chains. In

opposition to the results obtained for the polystyryllithium chains, the reaction is quantitative

and lead to the formation of well-defined PB stars. The molecular-weight data, the good

correlation between the intrinsic viscosity and the molecular-weight, and the fractionation

data allowed them to conclude to the complete stoichiometric coupling reaction between the

polybutadienyllithium chains and this family of chlorosilane compounds.

Fetters and Mortonl48 demonstrated in their case that the stoichiometric reaction of the

polyisoprenyllithium chains with tetrachlorosilane agent gives in maj ority three-arm stars.

From these previous results, it appears that the grafting reaction efficiency varies as

follow:

polybutadienyllithium > polyisoprenyllithium > polystyryllithium

Since the observed evolution is in opposition to the evolution of the intrinsic reactivity

of the living chains, it was concluded that only the steric hindrance generated as the coupling

reaction proceeds influences the reaction efficiency. To remedy this problem and thus









increase the yield of the coupling reaction in the cases of polystyryllithium and

polyisoprenyllitium chains, few butadiene units (average of five) were added before the

reaction with the chlorosilane compound. By this way, Fetters and Mortonl48 were able to

obtain in a quantitative manner four-arm PI star polymers using tetrachlorosilane as linking

agent.

Another way consists in the use of compounds which have halogenated silyl groups

separated by an alkyl chain. 1 ,2-bis(dichloromethylsilyl)- and 1 ,2-bis(trichlorosilyl)ethane

allowed Roovers and Bywaterl49150 to synthesize and study a series of four- and six-arm PS

stars. The addition of few isoprene units to the polystyryllithium chains allowed a

considerable decrease of the time needed for the quantitative obtention of four-arm stars and

was essential for the preparation of six-arm stars. Hadjichristidis and Rooversls used the

same linking agents for the preparation of four- and six-arm PI star polymers.

The synthesis of coupling agents of functionality equal to 8, 12 and 18 was done by

Hadjichristidis et al. 152,153 by adapting the synthetic strategy for the obtention of the desired

functionality (Figure 3-4).

The efficiency of the coupling reactions between the latter polychlorosilane agents and

polydienyllithium allowed the formation of well-defined star polymers with 8, 12, and 18 PI

branches. It should be noted that the authors advocated the addition of butadiene units to

increase the coupling reaction efficiency. By using this category of electrophilic agents,

Toporowski and Rooversl54 have obtained PS stars of 12 and 18 branches. In the latter case,

some triethylamine was added to decrease the coupling reaction time; indeed this additive

allowed the increase of the carbanionic species reactivity in hydrocarbon solvents.

These results confirmed that the reaction of chlorosilane derivatives with polymer

chains possessing a butadienylithium chain-end allowed the access to well-defined structures

and this even if the coupling agent functionality increases.









To prepare star polymers of largely higher functionality, Roovers et al. "5 had the idea

to use as linking agent third- and fourth-generation dendrimers possessing at their periphery

chlorosilane groups of same reactivity.156'157 The dendrimers were prepared starting with

tetravinylsilane and using two reactions, the hydrosilylation of the vinylsilane groups with

dichloromethyl silane and the nucleophilic replacement of silicon chloride by vinylmagnesium

bromide, as shown in Figure 3-5.

PB stars of 32, 64 and 128 branches could be synthesized. However, it should be noted

that the reaction for the preparation of 32- and 128-arm star polymers is very slow (8 weeks).

These works generated the best results obtained in the area of the star polymer synthesis

because of the very high number of branches and the good definition of these structures.

The use of methyltrichlorosilane and tetrachlorosilane has also been extended to some

other polymers. Ressia et al. "8 thus demonstrated that it was possible to obtain three- and

four-arm polydimethyl siloxane (PDMS) stars by using these coupling agents. In thi s case,

fractionation is needed to separate four-arm stars from three-arm stars. Mays and

colleaguesl59 prepared three-arm poly(cyclohexadiene) stars by deactivation of the

corresponding living chains on the methyltrichlorosilane.

In 1989, an original method capable of generating PB star polymers of several

hundred branches was described by the Roovers group.160 The synthesis took place in two

steps. First, the 18-arm PB stars containing a large majority of 1,2-PB units were

hydrosilylated to be modified into chlorosilane functions. In a second instance,

polybutadienyllithium chains were deactivated on these latter chlorosilane groups. By using

this strategy star polymers with an average of 270 branches were prepared. The coupling

reaction is very slow and this even in the presence of triethylamine as additive. It is also

impossible to precisely control the exact number of branches obtained which depends on the

yield of each of the two steps.









More recently, Quirk and colleagueS161 prOposed a new methodology derived from the

chlorosilane chemistry for the synthesis of star polymers utilizing the reaction of living

polymers with alkoxysilyl-functionalized polymers. After functionalization of a PS-b-oligoPB

polymeric organolithium compound with an excess of multifunctional chlorosilane linking

agent (1 ,2-bis(dichloromethyl silyl)ethane) in benzene, the resulting polymeric chlorosilyl

groups were converted to methoxysilyl groups with anhydrous methanol in the presence of

triethylamine to minimize linking reactions. Finally, a four-arm star-branched polystyrene

was prepared by treating methoxysilyl-functionalized PS-b-oligoPB with excess of PS-b-

oligoPBLi living chains (Figure 3-6). However, fractionation is still needed to separate four-

arm PS stars from the excess PS-b-oligoPBLi.

Halomethylbenzene compounds. The halomethylbenzene compounds is another

category of polyhalogenated agents which were used for star synthesis. Yen and Wengerl62,163

have demonstrated that the coupling reaction between 1,2,4-trichloromethylbenzene and

polystyryllithium species leads to a mixture of several populations, one corresponding to star

polymers of functionality higher than 3. The same procedure was also applied by Allen and

colleaguesl64,165 for the four-arm star polymer synthesis. For this purpose, the reaction was

carried out in a mixture of THF/Benzene (50/50) at high temperature in the presence of

1,2,4,5 -tetrachloromethylbenzene. In thi s case again, a mixture of polymers with functionality

in the range of 2 to 4 and even higher was obtained; the percentage of species with a

functionality higher than the targeted one was found around 40%.

From these previous studies, it was concluded that the low coupling reaction yield and

the formation of polymer with functionality higher than the theoretical one is due to a

secondary reaction. This latter is the halogen-lithium exchange reaction described below

(Figure 3-7).









This parasitic reaction generates in the reaction medium on the one hand chloride-

functionalized polystyrene chains and on the other hand a second carbanionic species

(RMetClx-1). The latter species can then react on the halide function of the coupling agent

(RClx) and thus lead to the formation of a coupling agent of higher functionality,

polystyryllithium chains being capable of reacting again with this new linking agent. Altares

et all 65 demonstrated that the coupling agent should be added on the polystyryllithium chains

and not the reverse. Processing in this way, only 7 % of the final product was contaminated by

star polymers of functionality higher than the expected one.

When carried out in dry THF, Bryce et all 66 deactivated polystyryllithium chains in

1,3,5 -trichloromethylbenzene. Meunier and Van Leemputl67 also used the same conditions in

the case of 1,2,4,5 -tetrachloromethylbenzene and hexaki s[p-(chloromethyl)phenyl]benzene .

In the latter cases, the star samples did not show any species of functionality higher than the

targeted one. The use of THF allowed the elimination of the halogen-lithium exchange

reaction. The same observation was reported by Yen who worked with potassium as counter-

in163

As described by Bryce et al.,166 the use of 1,3,5 -tribromomethylbenzene does not

allow the preparation of PS stars. They demonstrated that this reaction leads only to the

formation of a difunctional polymer. However, the multifunctional bromobenzene compounds

proved to be more efficient for some other polymers. Indeed, Pitsikalis et at. 168 recently used

tetrabromomethylb enzene for the preparation of poly(2-vinylpyridine) (PVP) and poly(methyl

methacrylate) (PMMA) stars (Figure 3-8). The deactivation reaction of the corresponding

living chains in THF at low temperature leads to the formation of four-arm stars. Other four-

and six-arm stars were synthesized by Lazzari et at 169 who resorted to 1,2,4,5-

tetraki s(bromomethylbenzene) and hexaki s(bromomethyl)benzene as coupling agents (Figure

3-8).









This arm-first method was also applied by Milllen and colleaguesivo for the synthesis

of core-shell nanoparticles consisting of a shape-persistent polyphenylene dendrimer as the

core and of different polymers PS, PI, PEO as mono- or double-shells. For example, mono-

shell systems were obtained by "grafting-onto" (arm-first) process attaching PEO chains to a

second-generation polyphenylene dendrimer with an average of 12 chloromethyl functions.

Well-defined PEO-functionalized polyphenylene dendrimers with molecular weights between

104 and 106 Da were prepared.

Phosphonitrile chloride compounds. Some other research groups turned towards an

other category of multifunctional electrophilic compounds. For example, Gervasi and

Gosnelll7 compared the coupling reaction efficiency of polystyryllithium chains with cyclic

trimer phosphonitrile chloride in the first case and bis(trichlorosilyl)ethane in the second one.

The first coupling agent allowed the formation of six-arm stars, whereas the second one gives

at best four-arm stars. These results could be surprising when compared with that of Roovers

et all172 However, the experimental conditions used by Gervasi and Gosnelll7 are different

since they did not add any additives and used a mixture of polar/apolar solvent which changes

the reactivity of the polystyryllithium species.

Multifunctional fluorinated coupling agent. More recently, Bates and colleagueS173

have investigated, a simple, unique method for star polymer synthesis. Living anionic

polyisoprene (PILi) chains were terminated by addition of hexafluoropropylene oxide

(HFPO). Through a series of fluoride ion (F~) eliminations (creating carbonyl groups) and

nucleophilic attacks by additional PILi chains, each molecule of HFPO coupled three chains,

forming regular three-armed stars (PI3) (Figure 3-9). The authors claimed that this strategy

eliminates the need for fractionation (in contrast to chlorosilane system) of the resultant

polymer since unreacted homopolymer and two-chain coupling products are negligible under

appropriate reaction conditions. However, complete coupling of PILi chains was never









observed using arm molecular weights higher than 5 kg/mol. Indeed, for larger molecular

weights, uncoupled PI chains and two-chain coupling products were observed by SEC.

Unsaturated multifunctional compounds. Allyloxy based compounds. Herz and

Straziellel74 were the first to employ allyloxy-based compounds, such as tri-(allyloxy)-2,4,6-s-

triazine (TT), as deactivating agent. After checking the efficiency of this latter linking agent

on the case of small organometallic molecules, this reaction was extended to

polystyrylpotassium chains. This method allowed the formation of three-arm PS stars with

narrow molecular wieght distribution. However, the presence of small quantity of linear PS

chains deactivated by impurities could not be completely avoided. By reaction of TT with the

tetraphenyl diisobutane, the same authors" obtained a tetrafunctional coupling agent which

result in the formation of four-arm star polymers.

Unsaturated multifunctional compounds. DDPE-type derivative. 1,3,5-Tris(1-

phenylethenyl)benzene was used by Quirk and Tsai20,176 a1s a linking agent for the synthesis of

a three-arm PS star, as shown in Figure 3-10. SEC and light scattering (LS) results showed

that the reaction is stoichiometric and complete leading to a well-defined star. Despite the fact

that the arm molecular weight used was rather low (Mn = 8.5 x 103 g/mOl), it can be concluded

that there is no steric limitation for the synthesis of three-arm PS stars using this coupling

agent. Previous efforts to use methyltrichlorosilane as a linking agent for the synthesis of

three-arm PS stars were not successful, due to incomplete coupling (steric hindrance effects).

Unsaturated multifunctional compounds. Fullerene. Soon after the discovery of

fullerenes, efforts were made to use C60 aS a coupling agent for the preparation of star

polymers. Samulski et al. 1 reported the reaction of living polystyryllithium chains with C60,

and later Ederle and Mathisl7 extended this work, providing mechanistic aspects on this

reaction in different solvents. In a nonpolar solvent such as toluene, it was found that by using

an excess of living PSLi chains over C60 a Six-arm star can be prepared by addition of the









carbanions onto the double bonds of fullerene. A similar behavior was observed when living

polyisoprenyllithium was used for the coupling reaction. In polar solvents such as THF a

different situation was observed. During the reaction of a living polystyrylpotassium with C60

in THF, a two-electron transfer was initially observed followed by the addition of four chains,

according to Figure 3-11.

However, in both types of solvents, the functionality of the product could be adjusted

by changing the reactivity and/or the steric hindrance of the living chain end. Thus, when the

living PS chains were end-capped with one unit of diphenylethylene (DPE), only the three-

arm star was produced. The functionality could be also controlled by the stoichiometry of the

reaction between the living polymers and C60. However, it was impossible to selectively

incorporate one or two chains per C60 mOleCUle.

3.2.1.2 Copolymerization with a divinyl compound

Divinylbenzene. The copolymerization between a difunctional monomer and living

anionic polymer chains is also another way to get star polymers with a large number of

branches. First considered by Milkovich,179 Rempp and colleagueslso described the synthesis

of star polymers by anionic copolymerization of styrene and divinylbenzene (DVB). Thus,

these star polymers are constituted of a cross-linked polydivinylbenzene core linked to several

PS chains which ensure the star solubilization. However, by using this way, star polymers

with large molecular weight distribution have been obtained.ls Moreover, the star polymer

samples were spoiled by a non-negligible quantity of linear PS indicating that the reaction

between living linear chains and double bonds was less probable as the polyDVB central core

is growing. This process led also to the same results when applied to the PI star synthesisl82

a large molecular weight distribution and the presence of linear chains. In 1969, Worsfoldl83

were able to obtain a more homogeneous molecular weight distribution for the star polymers

by using a pur para- or meta-DVB compound and benzene instead of THF.









However, it is still difficult to predict the number of branches linked to the polyDVB

core. All the previous studies demonstrated that the number of branches is dependent on

numerous parameters. Besides the ratio R = [DVB]/[Living chains], the length of the chain

precursors, the nature of the solvent (THF or benzene),183 the stirring conditions,184 the purity

and the composition of DVB,23 the temperature,'" and the chemical nature of the living

chains (styrene,183,186,187 butadiene, '5ls or cyclohexadienel89), COuld influence the

copolymerization reaction and at the same time the star preparation.

In conclusion, DVB is certainly useful for the preparation of star polymers of different

chemical nature and the coupling reactions are efficient for R values higher than 4. Even

though this method allowed the formation of star polymers with a number of branches varying

in a large range in function of the ratio R,184,185,187,188, 190-192 this is still impossible to obtain

well-defined structures.

Ethylene glycol dimethacrylate. Ethylene glycol dimethacrylate (EGDM) was also

used as comonomer for the plurifunctional cross-linked core synthesis, especially in the case

of PMMA stars. Indeed, in this latter case, the use of DVB and chlorosilane compounds is

unthinkable because of the low reactivity of the PMMALi living chains. The first example of

EGDM use was proposed by Zilliox et al~l82 who obtained PMMA star samples with large

molecular weight distribution. More recently, the same EGDM comonomer allowed

Efstratiadis et all 93 to prepare PMMA stars with a better structure definition, but only for arm

molecular weight higher than 40 kg/mol. Below this value, intermolecular coupling reactions

between different stars occurred giving samples with large molecular weight distributions.

Researchers from DuPontl94,195 prOposed, in their case, the synthesis of PMMA stars

by group transfer polymerization (GTP) using PMMALi living chains and EGDM as

comonomer at 85 oC. The same comonomer was employed by Helder and Milllerl96 foT

poly(t-butyl acrylate) (PtBuA) star synthesis.









However, as for the case of DVB, all the studieS182,193,195 TOSult in the same

conclusions, that is namely the number of branches in the star polymers depends on :

length of the living chains

the ratio [EGDM]o/[Living chains]o

reaction time of the living chains on the difunctional comonomer.

Moreover, the quantity of residual linear chains is decreasing with the polymer chain

length and increasing with the reaction time and the ratio [EGDM]o/[Living chains]o.

For example, the reaction of isotactic PMMALi living chains, initiated by t-

butylmagnesium bromide in the presence of 1,8-diazabicyclo[5.4.0]undec-7ene, with EGDM

comonomer led to the formation of star polymers with a number of branches estimated

between 20 and 30.197 In the case of syndiotactic PMMALi, Hatada et all 97 advocated the use

of butane-1,4-diol in place of EGDM to make easier the coupling reaction (obtention of star

polymers with number of branches ranging from 50 to 120).

3.2.2 "Core-first" Method

In this second method a multifunctional organometallic compound, that is capable of

simultaneously initiating the polymerization of several branches, is used in order to form a

star polymer (Figure 3-12). There are several requirements that a multifunctional initiator has

to fulfill in order to produce star polymers with uniform arms, low molecular weight

distribution, and controllable molecular weights. All the initiation sites must be equally

reactive and have the same rate of initiation. Furthermore, the initiation rate must be higher

than the propagation rate. Only a few multifunctional initiators satisfy these requirements, and

consequently, this method is not very successful. Complications often arise from the

insolubility of these initiators, due to the strong aggregation effects. The steric hindrance

effects, caused by the high segment density, causes excluded volume effects.









3.2.2.1 Multifunctional oxanionic initiators

These plurifunctional initiators possess hydroxyl functions which can, once

deprotonated, initiate the polymerization of oxirane monomers in a more or less efficient way

as shown by the different examples below.

The first example of PEO stars was reported in the literature by Gnanou et all 98 in

1988. In this paper, the authors propose three different methods to prepare PEO stars.

The first strategy results from the deprotonation of hydroxyl functions of

trimethylolpropane. The successive metalation of the alcohol groups has as consequence the

decrease of the precursor solubility. Indeed, once all the hydroxyl functions are deprotonated,

the multioxanionic species are totally insoluble. However, the addition of ethylene oxide in

the reaction medium leads to the formation of three-arm PEO stars.

The second one consists in the synthesis of a graft copolymer which can be considered

as a star polymer, if the pendant chains are largely longer than the polymer backbone. For this

purpose, potassium 2-alkoxide ethylstyrene was first polymerized to build the backbone. In a

second step, the alkoxide sites were used as initiators for the ethylene oxide polymerization.

The average number of PEO side chains obtained is close to 25.

The last method proposed consists in the reaction of naphtalene potassium with a

difunctional monomer such as DVB to form a microgel nodule covered by living anionic sites

which can be used as a multifunctional initiator. The ratio [DVB]/[K ] should be kept lower

than 3 in order to reduce the aggregation and to avoid a network formation.

PEO stars having 4, 8, and 16 arms were also prepared using hydroxyl-functi onalized

carbosilane dendrimers of several generations.199 For this purpose, the end groups of a

chloride-functionalized carbosilane dendrimer were converted to hydroxyl groups and were

activated using potassium naphthalene. The polymerization of ethylene oxide was initiated by

these active sites. The results of these methods confirmed the preparation of well-defined star









polymers with narrow molecular weight distributions. However, the tedious preparation of the

dendrimer core molecules is the only drawback of this method.

Hyperbranched polyglycerol and polyglycerol modified with short poly(propylene

oxide) chains, activated with diphenylmethylpotassium (DPMK), were also employed as

multifunctional initiators for the synthesis of PEO stars.200 Hyperbranched polyglycerol was

found to be an unsuitable initiator due to the strong association effects caused by its highly

polar groups. The incorporation of the poly(propylene oxide) chains (degree of

polymerization, 23-52) was crucial for the synthesis of the PEO stars. Moderate to large

molecular weight distributions were obtained ranging from 1.4 up to 2.2. The functionalities

of these stars were calculated to vary between 26 and 55.

Second-generation polyphenylene dendrimers functionalized with exactly 16

hydroxymethyl groups prepared by the Milllen group were also used as multiinitiator for the

living anionic polymerization of ethylene oxide to obtain well-defined core-shell

nanoparticles.170

3.2.2.2 Pluricarbanionic initiators

This category of multifunctional initiators, especially used for the polymerization of

vinyl and diene monomers, was not really successful compared to the multifunctional

initiators used in the other polymerization type such as radical controlled polymerization

(ATRP, RAFT, NMP, etc...).142 The tedious synthesis of precursors of higher functionality

and the low solubility of the pluricarbanionic species in different solvents are the main

reasons of this lack of interest. Moreover, even when the latter were soluble, the results

obtained after polymerization were in most cases disappointing.

The different examples of pluricarbanionic initiators reported in the literature were

already discussed earlier (Chapter 1). The only convincing example is the synthesis of a

tricarbanionic initiator proposed by Quirk and Tsai.20 This multifunctional initiator, was found









soluble in apolar solvents after reaction of 3 moles of sec-butyllithium with 1,3,5-tris(1-

phenylethenyl)benzene (tri-DPE) as presented in Figure 1-2. The efficiency of the

tricarbanionic species was demonstrated for the anionic polymerization of styrene and

butadiene, but always in the presence of polar additives to avoid the formation of polylithiated

species aggregates.20,21

3.2.2.3 Polythiolates initiators

Nicol et al.201 have first reported the synthesis of sulfur-containing star polymers by

anionic polymerization of propylene sulfide initiated with multifunctional thiols in the

presence of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) as the co-initiator. However, the lack

of diversity in multifunctional thiol structures, which originates from oxidative coupling to

form disulfides, reduces versatility in designing star poly(sulfide)s.

Endo and colleagueS202 prOposed in their case a novel trifunctional initiator

synthesized by reaction of a five-membered cyclic dithiocarbonate with benzylamine or

octadecylamine (Figure 3-13). The initiator system was constructed by addition of DBU,

which leads to the thiolates/thiols equilibrium through rapid proton exchange. Anionic

polymerization of propylene sulfide using trifunctional initiator/DBU system was carried out

in dimethylformamide (DIVF) at 0 oC and was quenched by 1-(chl oromethyl)naphtal ene,

which has been to be effective for termination of thiirane polymerization. The trifunctional

initiator efficiently initiated the polymerization of propylene sulfide to afford the

corresponding star-shaped polymers quantitatively with narrow molecular weight distribution.

3.2.3 "In-Out" Method

This method consists in resorting, in a first time, to the "core-first" method to generate

carbanionic sites, which could in a second instance initiate the polymerization of the same or

another monomer introduced in the reaction medium.27187191,203-207









Zilliox et at.Is were the first to employ this strategy. Indeed, after the preparation of a

stable polyDVB suspension by addition of PSLi chains on DVB, another styrene aliquot was

added in the reaction medium. However, large molecular weight distributions were obtained

for the different star samples and the control over the number of branches was not reliable.

In order to improve the control over the star structure by using this "In-Out" method,

Quirk et al.208 replaced DVB by a diphenylethylene derivative and studied the coupling

reaction of PSLi living chains with 1,3-bis(1 -phenylethenyl)benzene (MDDPE) followed by

the initiation of styrene polymerization by the carbanionic sites generated after the coupling

step (Figure 3-14).

The coupling reaction of poly(styryllithium) of various molecular weights with

MDDPE in benzene is a very efficient reaction when the stoichiometry of the reaction is

carefully controlled (yield > 96%). Because of the lack of reactivity of poly(dienyllithium)

chains in addition reactions with 1,1 -diphenylethylene units, it is necessary to add a small

amount of Lewis base such as THF for the formation of (PB)2-MDDPE targeted product.

After addition of a second amount of monomer, calculated to obtain the same monomer unit

number as for the initial branches, a four-arm PS star is obtained. Through their studies, they

demonstrated that the addition of Lewis base such as THF and s-BuOLi is needed during the

crossover reaction to prevent chain-end association behavior for these dilithium

macroinitiators in hydrocarbon solvent. Moreover, a minimum arm lengths of 3x103 g/mOl

(value determined by UV-Vis spectroscopy studies) is required for complete crossover

reaction of diphenylalkyllithium sites with styrene monomer. By comparing the samples

prepared with the ones obtained by coupling reaction with SiCl4, Quirk et al.208 COuld

conclude to the four-arm structure of the star polymers synthesized by this "In-Out" method.









3.2.4 "In-In" Method

The basis of the two-step "In-In" method209,210 iS as follows: star polymers with

polyDVB cores, synthesized by the arm-first method, include many unreacted double bonds

in their cores, and these double bonds can be attacked by the carbanions of some monomers

such as styrene and dienes (Figure 3-15). Therefore, in the first step of this method, a star-

shaped polymer with a polyDVB core is synthesized in the same way as an arm-first method.

In the second step, a known amount of the star polymer synthesized in the previous step is

dissolved in THF and added to living PS or polydiene chains. The carbanions located at the

end of the living linear chains attack the double bonds of the cores of the star molecule and

attach to them by reacting with these double bonds. However, for some monomers such as

alkyl methacrylate, vinyl pyridine, and ethylene oxide, which have higher electrophilicity than

styrene or divinylbenzene, the carbanions of these monomers cannot attack the double bonds

of the cores of the star molecules.

3.3 Results and Discussion

3.3.1 Application of Halogen-Lithium Exchange Reaction to Star Polymer Synthesis

We have exploited here the possibilities offered by this halogen-lithium exchange

reaction to prepare novel tri- and tetracarbanionic initiators for the synthesis of well-defined

three- and four-arm star polymers obtained by the "core-first" method.121 This method rests

on the metallation of poly(arylhalide)s whose halogens are carried by separate aryl rings.

Unlike regular halogen-metal exchanges, the metallation in our case could be conducted at

room temperature and in apolar medium for the polylithiated species formed, which were

unexpectedly found soluble in the presence of o/C1-coordinating ligands; this remarkable

feature could be further exploited for star synthesis.

To successfully demonstrate the viability/pertinence of our method, we have utilized a

commercially available diaryl halide (1) and have also designed two poly(arylhalide)s

carrying respectively three (2 and four (E halides. The two poly(arylhalide)s of functionality









3 and 4 have been obtained using reported procedures (see Chapter 7: Experimental Part).211-

213 2 was derived from the reaction of 4-bromoacetophenone diethyl ketal with acetyl chloride

using samarium trichloride as catalyst; as for 3, it was generated in excellent yields (> 90%)

by Diels-Alder reaction between 2,3,4,5 -tetraki s(p-bromophenyl)-cyclopentadienone and

phenylacetylene, carbon monoxide being extruded in this process. The expected structures of

the different multibromo co pounds were demonstrated by H NMR s ectra of 2 and 3 (see

Chapter 7: Experimental Part).

Next 1, 2 and 3 were subjected to reaction with stoichiometric amounts of sec-

but llithium in benzene to generate 1', ', 3', the corre ponding di-, tri-, and tetracarbanionic

initiators (Figure 3-16).

The formation of 2-bromobutane (4) which accompanies these reactions was

monitored by gas chromatography (GC) (see Chapter 7: Experimental Part). In the three cases

the yields were quantitative as only 2-bromobutane and the corresponding protonated polyaryl

compounds were found in the analyzed products. No coupling between 2-bromobutane and

the pluricarbanionic s ecies formed, 1', 2' or 3', was ever detected, indicating that in aolar

medium no such side reactions occurred. However, the resulting polylithiated species were

insoluble in benzene and therefore could not be used as such for initiation purpose, the

monomers tri ed-styrene, butadiene, 1,1 -diphenyl ethyl ene--fai ling to react with the se

aggregates. Various additives have thus been employed to solubilize these pluricarbanionic

species. Even though tetramethylethylenediamine (TMEDA) was able to solubilize the di- and

tetralithiated initiators, out of the additives tried the ligand that proved the most efficient at

solubilizing these carbanionic aggregates no matter their functionality was lithium 2-

methoxyethoxide (5 (Figure 3-17); this o/C1-ligand was previously employed by Teyssie and

colleagues214 to prevent lithium enolates from aggregating in apolar medium and by this

means bring about livingness in the anionic polymerization of methacrylic monomers. A ratio









of [lithium 2-methoxyethoxide] to [-PhLi] equal to 4 was necessary to obtain fully soluble

initiators in benzene (Figures 3-17 and 3-18). In these attempts at solubilizing 1', 2', 3', 5 was

prepared separately by reaction of sec-butyllithium with 2-methoxyethanol, but in the

polymerization experiments conducted subsequently 5 was simply generated in-situ by

addition of sec-butyllithium prior to the lithium-halide exchange undergone by 1, 2, or 3

(Figure 3-18).

Before triggering polymerization by monomer addition, we managed to neutralize 4

that resulted from the lithium-halide exchange reaction; even though 4 was inert enough not

to react with 1' 2', and 3', the poly(aryllithium)s formed, it is sufficiently electrophilic to

deactivate the growing carbanionic chains of polystyrene or polybutadiene. Indeed, in a

separate experiment conducted under stoichiometric conditions and in benzene we observed

the occurrence of such deactivation of polystyryllithium anions by 4 in the presence of

TIVEDA, the disappearance of 4 being complete in less than thirty minutes. To neutralize 4

prior to monomer addition one equivalent of sec-butyllithium was added and the formation of

3,4-dimethylhexane (6) that resulted was monitored by GC (see Chapter 7: Experimental

Part). The disappearance of 4, and the concomitant formation of 6 were monitored by gas

chromatography (GC) with trace of undecane as internal standard. After checking that the

neutralization of 4 was complete, the polymerization of styrene or butadiene could be

triggered upon addition of the corresponding monomers. Upon deactivation of the living

carbanionic chains by ethylene oxide after complete monomer consumption, co-hydroxyl

three- and four-armed pol strene and pol butadiene stars could be isolated from 2', and 3'

used as initiators (Figure 3-18). OE,c-dihydroxyl telechelic samples were obtained from 1'.

Analysis by gas chromatography and size exclusion chromatography (SEC) indicated

the complete consumption of initiators. No peak attributable to the presence of residual 1, 2,

or 3 could indeed be detected in the low molar mass region, the only trace seen being a









narrow and monomodal peak corresponding to the expected star or linear polymer in the high

molar mass region (Figure 3-19).

Such a narrow molar mass distribution (M /Mn <1.1) reflects a rate of initiation by

1', 2, or 3' comparable to that of propagation (Table 3-1). The structure of the polymer

formed and specially the star character could be established first by 1H NMR analysis using

polybutadiene samples of low degrees of polymerization (Figure 3-20). From the ratio of the

integration values due to the signal of the aromatic core (3= 6.8-7.3 ppm) to that of -CH2-OH

chain ends (3= 3.7 ppm) the actual functionality of the various samples prepared could be

determined: functionality values close to 3 and 4 were respectively obtained for the three- and

four-arm polybutadiene stars and close to 2 for the telechelics.

Characterization of both linear and star polystyrene and polybutadiene samples by

SEC equipped with a light-scattering detector (SEC-LS) also showed an excellent agreement

between experimental and expected values of molar masses.

Further evidence of the three- and four-arm star structure could also be obtained by

comparing the intrinsic viscosity [r] of our samples with that of linear polymers. Indeed, one

classical means to probe star-like architectures and their actual functionality is to determine g'

which represents [rlsta[r/[niinea. As can be seen in Table 3-1, the g' values calculated are close

to the ones predicted by theoretical models.215-217 These results thus confirm that the

structures initially targeted were actually obtained and validate the pertinence of our novel

approach of star synthesis by anionic means.

After demonstrating the efficiency of these di-, tri- and tetracarbanionic initiators for

the synthesis of polystyrene and polybutadiene telechelics and stars, (ABC)n (with n = 2, 3 or

4) linear and star block terpolymers were derived by sequential anionic polymerization of

st rene (S), butadiene (B) and meth 1 methac late (M) using 1', 2' or 3' as initiators. These

novel architectures-P(S-b-B-b-M)2 pentablock from 1', P(S-b-B-b-M)3 and P(S-b-B-b-M)4









star block terpolymers from 2' and 3', respectively--were actually prepared by the same

sequence of monomer addition as for the synthesis of P(S-b-B-b-M) linear block terpolymers

(Figure 3-21).218

Since lithium 2-methoxyethoxide (5) was present as an additive to solubilize ', 2' or

3' methyl methacrylate could be polymerized under living conditions--as disclosed by

Teyssie and colleagueS214-frOm polybutadienyllithium anions. Prior to the addition of M

polybutadienyllithium anions were end-capped with 1,1 -diphenylethylene (DPE) to reduce the

probability of side reactions on the ester group of M while initiating its polymerization. The

reaction medium was also diluted with tert-butylbenzene and the temperature decreased to -

400C to further prevent the above mentioned side reactions. Upon addition of M, the medium

turned from red characteristic of diphenylethyllithium carbanions to colorless. An aliquot

being sampled out before introduction of each type of monomer, the formation of these SBM-

based architectures could be easily followed by SEC (Table 3-2 and Figures 3-22 and 3-23).

The absolute molar mass of the first PS block could be obtained by SEC-LS; as for

PB and PM blocks their respective molar masses were deduced by 1H NMR spectroscopy

knowing that of their precursor (Table 3-2, Figure 3-24). In all cases narrow molar mass

distributions were observed for the three types of structures, attesting that the growth of the

three blocks occurred under living conditions. In some instances, P(S-b-B-b-M)n star block

terpolymers were contaminated with P(S-b-B)n precursors (less than 10%) but the latter could

be easily removed by fractionation through silica column.

3.3.2 Synthesis of Amphiphilic Star Block Copolymers Based on Polybutadiene and
Poly(ethylene oxide)

We present here the first synthesis of (PB-b-PEO)n (n = 3 or 4) amphiphilic star block

copolymers based on a polybutadiene core and poly(ethylene oxide) corona by anionic

polymerization.219 The divergent or "core-first" method appears to be the best route to prepare

such materials. The convergent method would require the synthesis first of PEO-b-PB-i+









linear living chains with a first block of PEO and a second block of PB, which is not known to

date. The only attempt to synthesize PB-b-PEO block copolymer with complex architecture

was the work of Xu and Zubarev,220 who prepared 12-arm PB-b-PEO heteroarm or miktoarm

star copolymers by the coupling of V-shaped PB-b-PEO chains to an aryl ester dendrimer

core; these were certainly not star block copolymers containing PEO blocks at the corona and

PB blocks at the core as in our case so that both bulk and solution properties would be

different. Previously, we presented the synthesis of novel tri- and tetracarbanionic initiators

based on a halogen-lithium exchange reaction and the example of well-defined three and four-

arm polystyrene and polybutadiene stars obtained by the "core-first" method.121

The preparation of (PB-b-PEO)n (n = 3 or 4) star block copolymers begins with the

transformation of the hydroxyl end groups in the (PB-OH)n (n = 3 or 4) star polymers (Figure

3-25). For this purpose, two star-shaped polybutadiene precursors were used as

macroinitiators for the PEO polymerization (Table 3-3). The polybutadiene stars were first

purified by freeze-drying in benzene or dioxane, and then reacted. A solution of

diphenylmethylpotassium (DPMK) in THF of known concentration, was then added dropwise

over a colorless solution of a known amount of (PB-OH)n (n = 3 or 4) in anhydrous THF to

titrate the hydroxyl end groups. At stoichiometry, a color change of the solution depending on

the initiator concentrations is observed. The macroinitiator solutions are green, red or yellow

for initiator concentrations of 1.5x10-3M, 6.25x10-4M or 3.15x10-4M, respectively. In addition,

the amount of (PB-OH)n (n = 3 or 4) macroinitiator, calculated from the molecular weight and

the mass of polybutadiene stars introduced in the flask, was used to confirm that such

titrations with DPMK were quantitative.

After titration, ethylene oxide was added to the (PB-O-K )n (n = 3 or 4) macroinitiator

solution as a liquid at -30 OC and the solution immediately became colorless. Then the

reaction mixture was heated to 45 OC and the polymerizations were typically run for 3 days to









ensure complete conversion of ethylene oxide. Deactivation of the "living" chains was

accomplished by the addition of acidic methanol (MeOH/HC1). Potassium chloride salts

(KC1) precipitated upon termination were isolated from the hydroxyl-terminated star block

copolymers by filtration. After concentration of the (PB-b-PEO),, (n = 3 or 4) solution on the

rotary evaporator, the block copolymers were precipitated in MeOH for the short PEO blocks

and in ethylic ether for the long PEO blocks and finally dried under dynamic vacuum.

All the data for the (PB-b-PEO),, (n = 3 or 4) star block copolymers are summarized in

Table 3-3. The recovered polymers were weighed, and the high yields demonstrate that the

conversion of ethylene oxide was near quantitative in all cases. Knowing the molar mass of

the PB core estimated by SEC/LS, the actual molar masses of the star block copolymer has

been determined by comparing the resonance signal at 6 = 3.6 ppm ((OCH2CH2)n (PEO

block)) with that at 6 = 4.8-6.0 ppm (protons of the double bonds (PB block)) (Figure 3-26).

A good agreement was found between the theoretical and experimental molar masses as

shown in Table 3-3.

The apparent molar mass values and polydispersity indices for the (PB-b-PEO),, (n = 3

or 4) block copolymers were measured by SEC in THF (Figure 3-27). A shift to high molar

masses with the disappearance of the (PB-OH)4 preCUTSor peak (see (PB76-b-PE0l725)4), ii

good control over the PEO molar masses and the relatively narrow polydispersities

(Mw/2,<1.32) indicate that the block copolymers obtained are free of any PB-OH star

precursors demonstrating that all hydroxyl groups of the (PB-OH)4 Star polymer were

deprotonated during the deprotonation step and that the alkoxides formed initiated the

polymerization of ethylene oxide. The broadening of the molar mass distribution after the EO

polymerization merely results from the fact that some alkoxides have a tendency to form

aggregates in equilibrium with unaggregated alkoxides.221









However, it can be seen that as the PEO molar mass per arm in (PB76-b-PEO444)4 and

(PB76-b-PE0l725)4 inCreaSCS molar mass distribution narrows with a symmetrical SEC trace

for the (PB76-b-PE0l725)4 Sample. In addition, we did not detect any amount of PEO linear

homopolymer (which could result from a slight excess of DP1VK in the reaction mixture)

even in the case of the samples with longest PEO blocks ((PB76-b-PEO444)4 and (PB76-b-

PE0l725)4) : they were indeed precipitated in diethyl ether and the presence of linear PEO was

never observed which would have been totally insoluble in diethyl ether as well. The same

observations were made in the case of the three-arm star block copolymers.

The amphiphilic character of the (PB-b-PEO)4 Star block copolymers was first

demonstrated by 1H NMR spectroscopy in CD2 12 and CD30D (Figure 3-28). Figure 3-28A

shows the resonance signals of both the hydrophobic and hydrophilic blocks in solution in

CD2 12, whereas Figure 3-28B shows that only the resonance signals corresponding to the

PEO hydrophilic block are observed in CD30D solution. The latter observation is consistent

with previous literature results that demonstrate CD30D is a good solvent for PEO blocks and

a non-solvent for PB blocks and as a consequence the formation of amphiphilic micelles in

CD30D with the PB core hidden by the PEO branches.222-22

3.4 Conclusion

In summary, halogen-lithium exchange reactions have been successfully applied to

generate di-, tri- and tetracarbanionic species from bis-, tris- and tetrabromoaryl compounds.

The use of a o/CL ligand was instrumental in obtaining polycarbanionic initiators soluble in

apolar medium and the subsequent preparation of various well-defined star-shaped

(co)polymers. These are the first examples of three and four-armed polystyrene and

polybutadiene stars obtained by the so-called "core-first" method using anionic

polymerization.121 Analysis of the macromolecular architectures obtained by different means

including SEC-LS, 1H N1VR spectroscopy and viscometry all endorse the star character and a










functionality of 3 and 4 for the samples derived from 2' and 3', respectively. The efficiency of

the latter was even exploited to synthesize (PB-b-PEO)n amphiphilic star block copolymers219

and P(S-b-B-b-M)n star block terpolymers (n = 3 or 4).121

The phase separation and morphologies that develop in such P(S-b-B-b-M)n star block

terpolymers could be investigated and compared with those reported for linear SBM

copolymers.225 Moreover, the good definition of the (PB-b-PEO)n amphiphilic star samples

allowed us to study their behavior either in aqueous solution or at the air/water interface.


Living
Polymerization


Multifunctional
Initiator


Je
~v~vv


Coupling
Reaction


Multifunctional
Coupling Agent


1) Linking
Reaction

2) Living
Polymerization


Je
~vv\N


Figure 3-1. General strategies for star polymer synthesis.
















Living polymer
chains


Multifunctional
Coupling Agent


F = function


Figure 3-2. Convergent method.


DifunctionalR
monomer





+n RR I


Living polymer
chains


Figure 3-3. Reaction of polymer chains with a difunctional monomer.




Cl3SiCH2CH2SiCl3 + 6 MNger I 6 CIMg~r + SiCH2CH


(I)


(I) + 6 HSiCl3 H2tl (C 3SiCH2CH2 3SiCH2Si(CH2CH2SiCl3 3


Figure 3-4. Synthesis of a coupling agent with 18 chlorosilane functions.










Excess of
I I PS-b-oligoPBLi
si-c2H4-Si-OCH3 >
OCH3 OCH3Bezn


Figure 3-6. Anionic synthesis of 4-arm star branched polystyrene
bis(dichloromethyl silyl)ethane as functionalizing agent.


using 1,2-


0 P Met + RClx Cl~C + RMetClx-1


Figure 3-7. Halogen-lithium exchange reaction.


BrH2C CH2Br

BrH2C CH2Br


4 /vvv +


+ 4 LiBr


PMMALi
PtBuMALi
P2VPLi


Figure 3-8. Synthesis of 4-arm star branched polymers using tetrabromomethylbenzene as
linking agent.


o 1)F F 3
F F
LI RT, 16h
2) MeOH


PILi


Figure 3-9. Synthesis of PI star polymer using HFPO as multifunctional coupling agent.


PS B1 ~ B PS
H3C--Si-C2H4--Si-CH3

PSfs B 13B ;PS








Li Li
PSH2C CH2PS
C6H5' Y C6H5

00Li
C6H5~ CH2PS


3 PSO OLi +


Figure 3-10. Use of 1,3,5-tris(1 -phenylethenyl)benzene as coupling agent.


C60 TH 2 PS' + C60 20 K THF ] pS-PS + C60 20 K )Z
25 oC 225 oC2


2 PSO OK +


4 PSS SK + C60 28 Kg THF
225 oC


Figure 3-11i. Use of fullerene C60 aS linking agent for star polymer synthesis.


Functional groups


Specific functions depending
on the polymerization type


F ,





Fs


F


+ nM


X X


Monomer


Multifunctional
initiator


Figure 3-12. Divergent method.










1) DBU/DMF
/-78 oC




00C, 2h
3) R'X/NEt3
RT, 1h


R/NH


H H


HSHO O SH
HS

R/NH


Cl

R'X = or CH3I


R= or ~CH2 fCH3


Figure 3-13. Synthesis ofthree-armed poly(propylene sulfide) star.


2 PS Lie +


PS, PS



Li / Li


PS\ PS





PS PS
O 8
Li Li


Figure 3-14. Synthesis of four-arm PS star by the "In-Out" method.















30 oC
THF


3 cnn 8/vvl .O +
LI
Living PS chains


Star polymer


Double star polymer


Figure 3-15. Application of the "In-In" method for star synthesis.


Br

LIBtOLi L i +2
4


Br Br es eun~e
1


Br~1


3 s-BuLi a
Benzene


LOi


Br Br 4 s-BuLi
Benzene


Br Br


oo~i+~Br


8
Li


Figure 3-16. Synthesis of dilithiated (1'), trilithiated Q', and tetralithiated Q') initiators.




















CH3 HC





CH3 HC--





Figure 3-17. Scheme of the tetracarbanionic initiator/lithium 2-methoxyethoxide o-C1
complex.


/ \ ~1)HO OH

Br Br ~~~~~2) s-BuLi 3L ~ iO OH
Benz ene 5


Br Br g 6
3 Li 3, L





3'HO/ /\ O



3) CHzOH


OH `OH



Figure 3-18. Synthesis of four-armed polystyrene stars.



















94






































38 40 42 44 46 48


28 30 32 34 36 38 40 42 44 46 48 50 52


na






d


34 36


Elution time (min)



Figure 3-19. SEC eluograms of (PS)4 pOlystyrene and (PB)4 pOlybutadiene stars : a)
protonated version of 3'; b) polystyrene star; c) polybutadiene star; and d) flow
marker.










h e f b d
- CH,- H- -H=H- HH-CH7- HCH
iCH


8.0 7. .5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
8 (ppm)


f b 8 d
-CH,-CH=CH-CH -CH,-CH -OH


h e
:H --C H-
b HC,
CH


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
8 (ppm)


Figure 3-20. 1H NMR spectra (CD2 12 ; 400MHz) of (PB-OH)4 (Mw,Ls 1800 g~mol l; 2\y'/2M,
= 1.1) and (PB-OH)3 (M~w,Ls = 2400 g.mol- ; 2y/M, = 1.1) hydroxyl terminated
star polymers.










00~ 0
Li Li

/ \

LI L


1) 5
2) Styrene
> (PS-Li )4
Benzene, RT, 12h


~~ P(S-b-B- Li )4
Benzene,
50C to RT, 24h


,Benzene, RT, 1h


P(S-b-B- Li )4


> P(S-b-B-b-M- Li ),


,tert-Butylbenzene, -40 oC, 1h


CH30H






Figure 3-21. Reaction scheme for the synthesis of SBM star block terpolymers.



P(S-2-B),


2~6 2~8 30O 3~2 3 4 36 3~8


Figure 3-22. SEC eluograms
copolymer.


Elution time (min)
monitoring the formation of a P(S-b-B-b-M)2 pentablock


CH,

2) o
OMe














P(5)z


P(5-b-B)3


P(S--B-B-M~,


1~'1 I III I
4U 42 44 4~ 4X




P~S),


IIIIIIIIIII
36 3X 40 42 44



P(S-BB),


I I I I I I I
34 36 3X 40 42


39 41 43 45


34 35 36 37 38


Elution time (min)



Figure 3-23. SEC eluograms monitoring the formation of a P(S-b-B-b-M)n (n = 3 or 4) star
block terpolymer: a) (PS)n polystyrene star; b) P(S-b-B)n star block copolymer;
and c) P(S-b-B-b-M)n star block terpolymer.












H)


7.5 7.0


6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5


8 (p pm)


Figure 3-24. 1H NMR spectrum (CDCl3, 400 MHz) of P(S-b-B-b-M)3 Star block terpolymer.

















CH K+


(PB-OH)4 >HR KO /~


~OK


1) ~,THF, 40 OC

2) H*, RT



~: Polyphenylene core

-------: Poly(ethylene oxide) block

: Polybutadiene block


Figure 3-25. Synthesis of (PB-b-PEO)4 Star block copolymers.









g e f b
::b2- HI-CH2-CH=CH-
CH2
c


d
-CH2 CH2-CH2-O CH2-CH2-OH


5 / (ppm)



Figure 3-26. 1H N\MR spectra (CDCl3 ; 400MHz) of a star copolymer (PB76-b-PEO444)4 (M~n,1H
NMR = 94600 g.mol l; 2y/2,= 1.22).
-- (PB-OH)4 prCCUTSor
x~- (PB,,-b-PEO,,)4


(PB,,-b-PEO444)















6 6.5 7 7.5 8 8.5 9

E lution tim e (m in)


Figure 3-27. SEC traces of the (PB-OH)4 preCUTSOT (2Ev,Ls = 16 400 g.mol l; 2y/2, = 1.05)
and of the star copolymers (PB76-b-PEO,,)4 (n = 57, 137, 444, and 1725) in THF.










A)


7.0 6.0 5.0 4.0 3.0 2.0 1.0











7.0 6.0 5O 0 .0 3.0 2.0 1.0
8 (ppm)


Figure 3-28. 1H NMR spectra (200MHz) of (PB76-b-PEO444)4 in CD2C 2 (A) and in CD30D
(B).










Table 3-1. Characterization of PS and PB samples synthesized from 1', 2' and 3' initiators, respectively.


g' (theo)
Mn [b] M [ai My /Mn [b] Mn tho[c][] g' [e] Zm-[
Stock mayer[ ri Berryl~ Gr est[ h]

PS2 11000 11200 1.12 12000 1.9
80900 90800 1.08 89000 3.0 0.805 0.91 0.88 0.99
PS3
96700 131000 1.13 128000 3.0 0.846 0.91 0.88 0.99

31200 38400 1.08 39500 3.9 0.75 0.83 0.79 0.79
PS4
84700 98600 1.08 120000 3.9 0.79 0.83 0.79 0.79

PB3 25100 32500 1.03 30000 3.0

PB4 9400 16400 1.05 17200 3.9


[a] Determined by SEC in THF using a multiangle laser light scattering detector. The dn/dc value was taken equal to that of linear polystyrene
(dn?/dc = 0.183cm3/g in THF). [b] Derived from refractometric detector. [c] Mn (theo) = Msttyrene X ([Styrene]/[-PhLi]) x n (n = 2, 3 or 4). [d]
Average functionality of the samples as determined by 1H NMR. [e] Experimental values of : g'= [rlstar/[rliinear. [f] g'R.W. = (2/f) [50.396(f-1)+
0.196]/0.586.215 [l_' g'R.W.0.5 = [(3f-2)/f2 0.5 216 [h] g'= K'.FP (K=2.37 and p=-0.789).217





















Table 3-2. Characterization of P(S-b-B-b-M)2 pentablock, P(S-b-B-b-M)3 and P(S-b-B-b-
M)4 Star block terpolymer samples.


PS P(S-b-B) P(S-b-B-b-M)
Microstructure

M~ lal y/n[]M NM M b Mn [ My /Mn [b (%1,2-(B))[d]

(SBM)2 30000 1.09 35000 1.1 41000 1.2 60

(SBM)3 2800 1.08 5700 1.1 7500 1.1 75

(SBM)4 6100 1.05 12100 1.1 16100 1.2 70

[a] Determined by SEC in THF using a multiangle laser light scattering detector. The dn/dc
values of PS was 0.183 cm3/g in THF. [b] Derived from refractometric detector. [c]
Determined by 1H NMR from the molar mass of the polystyrene block, assuming 100%
efficiency in the initiation of the second and third blocks. [d] Calculated by 1H NMR.










Table 3-3. Characteristics of hydroxyl functionalized (PB-OH), star polymers and (PB-b-PEO),, (n = 3 or 4) amphiphilic star block
copolymers.


(PB-OH) star precursors Amphiphilic (PB-b-PEO) star copolymers


Stars M, a) b,) Mgd) Mn~tim) B',2 M,a) Mn~estd) Mn,tif) Ms/M~a) Code

45900 42500 40500 1.2 (PBann-b-PEO76)3
56000 75500 77500 1.15 (PBznn-b -PEO326)3
(PB-OH)3 32500 1.03 31000 33000 76
58000 160500 164500 1.2 (PBznn-b -PEO97())3
74000 320500 323000 1.2 (PBznn-b-PEOzl 82)3


28300
29400
34500
45800


26200
40600
94600
320000


27000
41500
96000
318000


1.23
1.32
1.22
1.19


(PB76-b -PE057)4
(PB76-b-PE0137)4
(PB76-b-PEO444)4
(PB76-b-PE01725)4


(PB-OH)4 16400


1.05 15000 17000


Determined by SEC in THF equipped with a multiangle light scattering detector. The dn/dc value was measured in THF (dn/dc
0.094 cm3/)
Apparent molar masses determined by SEC in THF using a polystyrene calibration.
Mrn,tiz = MButadiene x ([Butadiene]/[-PhLi]) x n (n = 3 or 4).
Estimated by 1H NMR analysis.
Mrn,tiz = MEo x ([EO]/[(PB-OH)4] + M11,(PB-OH)n









CHAPTER 4
TWO-DIMENSIONAL POLYMERIC NANOMATERIALS THROUGH CROSS-LINKING OF
POLYBUTADIENE-B-POLY(ETHYLENE OXIDE) MONOLAYERS AT THE AIR/WATER
INTERFACE

4.1 Introduction and Literature Overview

The idea of stabilizing amphiphile self-assemblies by polymerization was introduced at

least 30 years ago for monolayers and about 10 years later for bilayer vesicles.226,227 This

emerging approach to bridging the nanoscale world of labile, interfacially driven self-assemblies

with the meso-scale has resulted in several examples of massively cross-linked 3D structures.228

232 For example, Bates and colleagueS228 were the first to succeed in retaining the cylindrical

morphology formed by gigantic wormlike rubber micelles of polybutadiene-b-poly(ethylene

oxide) PB-b-PEO diblock copolymers in water by chemical cross-linking of the PB cores through

the pendant double bond of the 1,2-polybutadiene units (Figure 4-1) using water-soluble redox

combination of potassium persulfate (K2S20s) and sodium metabisulfite (Na2S20s)-ferrous

sulfate (FeSO4.7H20) for the initiation of cross-linking. This type of free-radical initiator, used

extensively in emulsion polymerizations,233 is ideally suited for generating a specified number of

radicals in the aqueous phase that are subsequently captured by the nanoscopic micelles. In this

work, the authors produced a relatively high concentration of radicals, one for every two PB

double bonds, thereby ensuring a high degree of cross-linking without disruption of the

cylindrical morphology. Although they have not determined the exact cross-link density for the

chemically fixed micelles, experiments indicate that every block copolymer has been covalently

bonded together within individual giant wormlike molecules. For example, extraction with

chloroform, which efficiently removes unreacted block copolymers from aqueous solution, fails

to recover any detectable PB-b-PEO linear diblock copolymers from the cross-linked system.









The Bates group232,234 also proposed the fabrication of massively cross-linked and

property-tunable membranes by free-radical polymerization of self-assembled, block copolymer

vesicles-polymersomes (Figure 4-2). They described a PB-b-PEO diblock copolymer that has a

hydrophilic weight fraction like that of lipids and forms robust fluid phase membranes in water.

The polymersomes sustain free radical polymerization of the hydrophobic butadiene, thereby

generating a semipermeable nano-shell. Cross-linked giant vesicles proved stable in chloroform

and could also be dehydrated and re-hydrated without modifying the ~9 nm thick membrane

core; the results imply defectfree membranes many microns-squared in area.

However, relatively few groups have shown interest in stabilization by cross-linking of

two-dimensional (2D) copolymer self-assemblies formed at the air/water interface; most studies

have involved interfacial polymerization of small molecules in Langmuir monolayers.235-263

In the early 1970's the group of Veyssie235,237,240,241 was the first to demonstrate the

formation of 2D cross-linked material by cross-linked polymerization of monolayers of

dimethacrylates, and several other difunctional reactive amphiphiles under UV irradiation at a

constant surface pressure at the air/water or oil/water interface. This idea was further followed by

other groups. Regen and colleagueS238,239 introduced the concept of a 2D-network of molecular

pores, i.e., "perforated monolayers" derived from calix[n]arene-based amphiphiles. For this

purpose, they employed a series of derived calix[n]arene-based amphiphilic surfactants

(mercurated calix[n]arene,238,239 thio-, amide-, thioamide- or imine-functionalized

calix[n] arene,244-246 Or unsaturated calix[n]arene245) to form stable monolayer at the air/water

interface (Figure 4-3). By polymerization of the calix[n]arene-based molecules either by

introduction of a cross-linking agent such as malonic acid (Figure 4-3B) or via UV irradiation,

they were able to synthesize porous and cohesive "perforated monolayers" (pore diameters in the









range 2-6 A+) that can function as molecular sieves for gas permeation selectivity (Figure 4-

3A).245,246

The Michl group252,259 prOposed the preparation of 2D grids through 2D supramolecular

chemistry. The general strategy consists in the linear coupling of arm-ends of star-shaped

monomers forced to adhere to a surface (mercury surface in this case) with their arms parallel to

the surface. After the polymerization of the star-shaped monomer (for example, the anionic

lanthanum sandwich complex of tetrapyridylporphyrin, Figure 4-4b) by introduction of a

coupling agent (p-xylylene dibromide, Figure 4-4a) by diffusion from a solution contacting the

surface, well-defined covalent 2D square- or hexagonal-grid polymers could be synthesized

(Figure 4-4c and d).252,259,264 They also proposed the preparation of 2D grids through cation-

bonded or hydrogen-bonded supramolecular chemistry.265-267

Palacin and colleagueS242,243,247 also designed supermolecular assemblies of amphiphilic

porphyrins by molecular engineering through molecular recognition between oppositely charged

monomers at the air/water interface. Two porphyrin monomers P2 and P3 bear four positive

charges while the third porphyrin monomer Pi bears four ionizable carboxylic functions (Figure

4-5): via an acid/base reaction between the funtional groups of each macrocycle, spatially

oriented flat-lying heterodimers P1-P2 and P1-P3 are Spontaneously formed at the air/water

interface.

Kloeppner and Duran254 were the first to demonstrate mechanical properties sufficient to

allow the removal of free standing fibers from the water surface a 2D cross-linked 1,22-bis(2-

aminophenyl)docosane (BAD) polyanilines. For this purpose, the oxidative polymerization of

BAD at the air/aqueous interface was done in the presence of a strong chemical oxidant,

ammonium peroxydisulfate, and an acid (sulfuric acid). The polymerization was monitored by

observing the barrier movement needed to maintain a specific applied surface pressure, assuming









that the polymerization rate can be calculated from the change in the area of the surfactant at a

constant surface pressure.

O'Brien and colleagueS226 described three different approaches (thermal with AIBN,

redox with potassium persulfate or sodium bisulfite, or photoirradiation polymerizations) to

polymerize monomeric lipids in a two-dimensional assembly proceeding in a linear or cross-

linking manner depending on the number of polymerizable groups (double bonds) per monomeric

lipid. Lipids that contain a single reactive moiety in either of the hydrophobic tails or associated

with the hydrophilic head group yield linear polymers. Polymerization of lipids with reactive

groups in each hydrophobic tail generally yield cross-linked polymeric networks.

Teyssie and colleagueS260,262 prOposed the first spontaneous styrene sulfonate

polymerization in Langmuir films following an anionic mechanism. Indeed, when a

dioctadecyldimethylammonium bromide (DODA) monolayer is spread over styrene sulfonate

(SSt) aqueous solution, this monomer was shown to undergo a spontaneous polymerization

process. This process was followed by monitoring the surface pressure variations at constant

molecular area and/or the molecular area variation at constant surface pressure versus time. The

spontaneous polymerization characteristics depend upon the monomer concentration, the surface

pressure, the subphase ionic strength and pH. The polymerization occurring at the interface with a

probable anionic mechanism is inhibited by carbon dioxide, sodium bicarbonate and LiCIO4.

Finally, Carino et al.257,258,263 followed the 2D gelation during the polymerization of

alkylalkoxysilane molecules under acidic conditions at the air/water interface by monitoring the

mean molecular area decrease and the surface viscosity increase versus time as the monolayer

was cross-linked. They also used brewster angle microscopy to show the complete coverage of

the water surface by the cross-linked material at the end of the reaction (Figure 4-6).









Concerning the cross-linking between true amphiphilic copolymeric chains at the

air/water interface, only one example based on a polymerizable lipopolymer was previously

proposed by O'Brien and colleagues.268 The amphiphilic copolymer investigated had a linear

hydrophilic backbone consisting of poly(ethylene imine-co-ethyl oxazoline) and containing 20 %

of hydrophobic sorbyl side chains, making it capable of forming stable Langmuir monolayers

(Figure 4-7). Network formation after photopolymerization of the sorbyl moiety upon UV light

exposure was demonstrated by monitoring the surface dynamic shear modulus (elasticity

measurement). Unfortunately, they were not able to characterize the 2D morphologies obtained

before and after the cross-linking reaction.

4.2 Interfacial Behavior of (PB-b-PEO)n (n = 3 or 4) Star Block Copolymers at the
Air/Water Interface

Amphiphilic block copolymers containing both hydrophilic and hydrophobic segments

form an important class of materials due to their wide variety of potential applications as

polysoaps, polymeric surfactants, solution modifiers, emulsifiers, wetting agents, foam stabilizers

and drug carriers.269-271 In mOst of the above areas, controlling the size as well as the surface

properties of block copolymer assemblies is a major issue. In this chapter, we investigate star

copolymers containing poly(butadiene) (PB) blocks.

The amphiphilic character of block copolymers has also been widely exploited for the

preparation of monolayers at the air/water interface. These monolayers are somewhat different

from classical low molecular weight amphiphiles in that the copolymer is constituted of

hydrophilic and hydrophobic blocks of considerable molecular weight. The hydrophilic block by

itself would be soluble in water, but the hydrophobic block acts as a buoy, anchors the polymer

chains at the interface, and thus prevents the hydrophilic part from dispersing into the bulk water

subphase. Numerous studies published on the field of monolayers at the air/water interface during









the past years demonstrate the utility in using the nonelectrolyte poly(ethylene oxide) (PEO)

water soluble block due in particular to its properties and its biocompatibility and subsequent

potential for applications in drug-delivery and other fields. Among copolymers investigated at the

air/water interface, polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymers

certainly form the most commonly studied systems.272-29

Although PS is a convenient choice due to its inexpensive price, monomer availability,

and facile synthesis, polybutadiene-b-poly(ethylene oxide) (PB-b-PEO) is the primary

amphiphilic diblock copolymer studied to provide control over spherical rodlike and vesicular

architectures in bulk or aqueous solutions.228,234,291,292 Furthermore polybutadiene offers the

possibility to stabilize block copolymer assemblies by cross-linking through the pendant double

bond of the 1,2-polybutadiene units.

However, in spite of the significant interest showed for PB-b-PEO copolymers, few

groups have studied the behavior of such amphiphiplic copolymers at the air/water interface.293

295 Among these, only Discher and colleagueS293 were able to show characteristic morphological

organization of this amphiphile at the air/water interface through AFM images, and were the only

ones who attempted crosslinking stabilization. Moreover, the behavior of any PB-b-PEO diblock

copolymer with architecture more complex than linear chains, whether in bulk, in solution, or at

the interface has not yet been investigated.

The structure of the AB diblock copolymers either in the bulk state or in solution is most

certainly influenced by the volume fraction of each block and by the segment-segment interaction

parameter X, but the molecular architecture, the conformational asymmetry and the compositional

fluctuations all also have an effect on structure.296 Systematic investigation of the influence of all

these factors on the organization of AB diblock copolymers in a star architecture necessitates the









preparation of monodispersed materials with well-defined molecular weights, block volume

fractions and architecture.297

4.2.1 Surface Pressure-Area Isotherms

Surface property characterization of the four different (PB-b-PEO)4 Star block copolymers

started with isotherm measurements. Figure 4-8 shows the surface pressure-area (n-A) isotherms

(250C) on compression with a log scale on the x-axis for convenient visualization. The isotherm

of each copolymer was reproducible and independent of spreading solution concentration.

Together, the isotherms revealed several characteristics. First, all the monolayers were

compressible up to surface pressures beyond 30 mN.m l. Second, all of the isotherms are

characterized by the three distinct regions illustrated in the cartoons of Figure 4-8: at high

molecular areas the so-called "pancake" region (I), a pseudoplateau (II), and the brush region

(III) at low surface areas. The dotted lines in Figure 4-9 also shows the extrapolation used to

estimate the three corresponding parameters Apancake, Ao, and AA. Third, the pressure of the

pseudoplateau region was very similar for all samples, while its width varied systematically. In

fact at the highest PEO composition, the pseudoplateau represents more than a 50-fold

compression. Fourth, the copolymers (constituted from the same PB core and different PEO chain

lengths) occupied similar areas in the high pressure brush region, independent of the PEO chain

length.

Considering the affinity of PEO for the air/water interface and the hydrophobicity of PB,

we suppose that the expanded surface film at large molecular areas (I) corresponds to a film

dominated by the behavior of PEO at the surface. Quantitative comparison of Apancake, the area

occupied by the pancake-like PEO domains when adsorbed at the air/water interface, supports

this interpretation. A fit of the data revealed a linear dependence of Apancake With the number of









EO units (y = 1.399x + 113.09; R2 = 0.989) indicating that the "pancake" region area was largely

dependent on the PEO block length (Figure 4-10).

Second, as the monolayer is compressed, a pseudoplateau is observed at a pressure of

about 10 mN.m- which is a signature of adsorbed EO monomer units at the air-water

interface.298,299 The length of the PEO block clearly influences the length of the pseudoplateau

(AA) as seen in Figure 4-11. In fact, a fit of AA with the number of EO units gives the very good

linear dependence (y = 0.6136x-6.0107; R2 = 0.999) shown by Figure 4-11. The magnitude of

the slope, 61 A2/EO repeat unit, is reasonable for EO units lying flat at the interface. The

observed linearity and small intercept implies that the change in area between Apancake and Ao can

be interpreted by PEO segments being successively submerged into the water subphase during

compression at approximately 10 mN/m along the pseudoplateau. This is also in qualitative

agreement with previous studies on analogous PS-b-PEO star block copolymers at the air/water

interface.282'283

Upon further compression, a second large pressure increase is observed up to values of 32

mN.m- a trend also observed in the case of PB-b-PEO linear block copolymers.293,294 In this

regime of high density, a brush conformation is expected. The latter is supported by the

theoretical area Ao that a compact film would occupy at zero pressure. Table 4-1 reveals that the

occupied surface area Ao is effectively the same for all the four samples (Ao/molecule = 32 + 4

nm2). The low area per butadiene repeat unit is a strong indication that the PB units have been

compressed into a 3D structure rather than lying flat at the air/water interface. This result also

confirms that only the PB segments have an effect on the brush region since the copolymers

synthesized all possess the same PB core size.









4.2.2 Film Relaxation

By hysteresis experiments, we then investigated the ability of these four arm (PB-b-PEO)4

stars to relax to the same area as that occupied in their original uncompressed state. We examined

the effects of pressure variation, compression/expansion cycles and the PEO block length on the

degree of hysteresis and these results are shown in Figure 4-12.

Pressure variation. As shown in Figure 4-12A, at low pressures (H < 8 mNm )~, only

minimal hysteresis was observed on compression and expansion, indicating that the surface films

were capable of expanding at the same rate as they were compressed independent of the PEO

block length. Thus, the star copolymers are elastic and highly surface active in the low pressure

region I.

For pressures in the range of 10 mN.m-l a dramatic increase in hysteresis was observed

with increasing pressure as shown in Figure 4-12B and C. This trend is consistent with the

interpretation that a higher surface pressure (H 210 mN.m l) is necessary to start to submerge the

higher molecular weight PEO branches into the water subphase. The observed

compression/expansion curves also indicate that the surface film now relaxes at a slower rate than

the compression.

Compression/expansion cycles. Hysteresis also changed with repeated

compression/expansion cycles. At lower pressures (H < 8 mN.m- ), the hysteresis remained

relatively minor and independent of the number of compression-expansion cycles applied. In

contrast, at higher pressures, the degree of hysteresis, the width of the pseudoplateau, and the

pancake limiting area systematically changed. The large initial hysteresis in Figure 4-12B-left

may indicate reorganization of the high molecular weight PEO arms between the first and second

compression. Subsequent creep to smaller surface areas indicate that with each cycle, slightly









more PEO is submerged into the water subphase and does not resurface over the time of the

experiment. However, we observed at higher pressures (TI > 10 mN.m- ) that for samples

consisting of very long PEO chains ((PB76-b-PE0l725)4 ; Figure 4-12C-left), the compression

curve of one cycle does not match the expansion curve of the previous cycle, but match the

compression curve of the previous cycle, unlike short PEO sample. In this last case, it could be

supposed that because of the very long PEO blocks, it is very difficult to submerge all EO units

into the water subphase and some could resurface at the air/water interface upon expansion.

4.2.3 AFM Characterization of the Transferred Monolayers

Atomic Force Microscopy was used to study the morphology of surface films at the

air/water interface after transfer to a solid surface. To this end, Langmuir-Blodgett films of two

different samples (PB76-b-PE0l725)4 and (PB76-b-PE057)4 were transferred to mica substrates

over a range of pressures. Table 4-2 and Figure 4-13 shows that for applied surface pressures

below 9 mN/m, positive transfer ratio values of approximately 1.0 were observed indicating

"ideal" transfer with no change in macroscopic film dimensions. Whereas surface pressures

above 8 mN/m lead to transfer ratios of approximately 2.0, or significant densification of the

surface film upon transfer. In all cases LB transfers were characterized by a linear instantaneous

transfer ratio indicating that the monolayer was transferred uniformly over the entire mica

sub state.

Due to the hydrophilic nature of the mica, we assume PEO transfers as the bottom layer,

represented in the scanned images as the continuous dark phase, whereas PB occupies the top

portion of the film corresponding to the white higher elevation microdomains shown in Figure 4-

14.









Effect of surface pressure. First, an effect of the surface pressure can be seen (Figure 4-

14) in the "pancake" region for the sample with the longest PEO blocks. At lower pressures (H =

2 mN.m- ) the PB microdomains are not homogeneous in size. However, when increasing

pressure from H = 2 mN.m-l to 8 mN.m-l the PB microdomains are more organized, of larger size

and less numerous for a same area. These observations were confirmed by the quantitative

analysis of the AFM scans shown in Table 4-3. In comparing AFM scans (Figure 4-14A D),

first a gradual increase in the diameter of PB domains (from 61 to 132 nm), their height (from 2

to 5 nm), and in the number of molecules per PB domain (from 4 to 186), and second a decrease

in the number of PB domains (from 445 to 18) and in the PB coverage (from 32% to 6%) with

the surface pressure increasing were observed (Table 4-3).

The above trend is also observed in the molecules/domain vs. pressure curve of Figure 4-

15, which shows more molecules continually aggregating (dramatic increase above pressure H =

4 mN/m) to form larger circular 2D micelles. This data is a strong indication that the surface

micelles formed on spreading the PB-b-PEO stars are fluid and dynamic at the air/water interface

in sharp contrast to PS-b-PEO systems where vitrification of PS leads to frozen surface micelles.

The AFM data also show that during compression, the distance between the PB

microdomains increases from an average distance of 70 nm at H = 2mN.m-l to 540 nm at H =

8mN.m- The estimated theoretical length of one extended PEO branch (1725 EO units and

assuming 3.19 A per EO unit) is about 550 nm, which is very close to the average distance

between two PB microdomains at H = 8 mN.ml (540 nm) illustrated in Figure 4-16.

At higher pressures (H > 8 mN.m- ), a second type of morphology is observed (Figure 4-

14E H). This change in morphology is mirrored by a significant increase of the transfer ratio

(T.R.) illustrated in Figure 4-13. The sudden jump in T.R. from 1.0 to 2.0 implies significant









densification of the film upon transfer in the pseudoplateau region (H > 8 mN.m- ). The AFM

data show that at H = 9 mN/m, PB microdomains are spaced much more closely compare to H =

8 mN/m and then form elongated stripes, or chains, at H = 10 mN/m. The onset of the chain

morphology correlates with the onset of significant hysteresis (Figure 4-12C) observed with the

PE0l725 blocks. Moreover, neither the chain morphology (Figure 4-14I and J) nor the same

hysteresis (Figure 4-12C) is observed for the shorter PE057 material, indicating a PEO length

influence chaining aggregation.

The observed results led to the model shown in Figure 4-16 for the (PB76-b-PE0l725)4

block copolymer. At low pressure, microdomains of polydisperse size, some 2 nm vertical

thickness, and few polymer chains per domain are observed. The relatively low density of PEO

chains allows these domains to be closely spaced and the PEO chains to be in a relatively

compact conformation. Upon compression the PB domains clearly flow and coalesce to form

progressively larger surface micelles of more monodisperse size and higher and higher PEO

chain densities that should lead to an overall extension of the PEO segments. We suppose that

reduction in the line tension between the PB and PEO rich phases helps drive the aggregation.

This process also increases the vertical thickness and significantly increases the lateral spacing

between domains. At higher surface pressure (H > 8 mN.m- ), and perhaps also associated with

compaction during LB transfer, we suppose the PB microdomains start to chain as illustrated in

Figure 4-16C. During chaining we hypothesize that the long PEO chains are further extended in a

direction perpendicular to the chain axis and this hinders spherical aggregation and favors

aggregate through points of contact at opposite ends of the elongated domain. Similar surface

morphology has also been observed in the case of PB-b-PEO linear block copolymers.293 At









higher applied surface pressures, we suppose that the remaining PEO chains are hydrated and

larger aggregates are formed, quickly leading to thicker films.

In contrast, we suppose that the short PEO branches of the (PB76-b-PE057)4 material are

much more easily submerged into the water subphase at higher pressure, and micelle chaining is

hindered.

4.3 Cross-linking of Polybutadiene-b-Poly(ethylene oxide) Monolayers at the Air/Water
Interface

We are interested in crosslinking monolayers of block copolymers to achieve porosity at

the submicron scale. Here, a 2D polymeric nanomaterial consisting of a continuously cross-

linked polybutadiene material with poly(ethylene oxide) domains of controlled size trapped

within the PB network is illustrated. The strategy opens up the possibility to retain a specific

morphology at the mesoscopic scale defined by a given surface pressure (n). Such porous

polymer thin films have potential applications in the preparation of membranes which will show

large differences in permeability to water, methanol, and other polar compounds depending on

the effective PEO "pore" size.

With this in mind, we investigated two different methods for forming 2D cross-linked

monolayers with a (PB-b-PEO)3 amphiphilic star block copolymer material based on a

polybutadiene core and a poly(ethylene oxide) corona. In the first method, cross-linking of the

PB hydrophobic block was achieved by using AIBN as a radical initiator under UV light directly

at the air/water interface. The second method was based on the self-condensation of the

triethoxysilane-functionalized polybutadiene blocks of the (PB(Si(OEt)3)-b-PEO)3 Star block

copolymer under acidic conditions. The latter route is extremely general and should be applicable

to functionalization and coupling via other silanes and metal alkoxides. In both cases, the surface

properties of the cross-linked materials were characterized by surface pressure measurements









such as surface pressure-mean molecular area (MMA: interfacial area occupied by one polymer

molecule) isotherms at different reaction times and isobar experiments (MMA evolution versus

time for a given 7C) at different subphase pH values. The monolayer morphologies obtained at

different surface pressures were studied by atomic force microscopy (AFM) imaging the

Langmuir-Blodgett (LB) films obtained before and after cross-linking.

4.3.1 Interfacial Behavior of (PB-b-PEO)3 Star Block Copolymers

We first investigated the surface properties of monolayers of a new set of (PB-b-PEO)3

amphiphilic three-arm star block copolymers at the air/water interface. A divergent anionic

polymerization method yielded copolymers with well-defined architecture, molecular weights,

and block volume fractions (Chapter 3). Different samples of well-defined (PB-b-PEO)3

amphiphilic star block copolymers exhibiting narrow molecular weight distributions were

prepared with poly(ethylene oxide) coronas over a broad range of volume fractions (Table 4-4).

Isotherm experiments at the air/water interface showed three characteristic regions: a "pancake"

region (I) at high mean molecular areas where slowly increases as the monolayer is

compressed, a pseudoplateau at a pressure of ca 10 mN/m (II) that corresponds to the dissolution

of the PEO chains and finally a compact brush region (III) at low surface areas affected only by

the PB segments (Figure 4-17). A fit of the pseudoplateau data revealed a linear dependence of

AA with the number of EO units (y = 12.351x 0,4889; R2 = 0.99) indicating that the

"pseudoplateau" region area was largely dependent on the PEO block length (Figure 4-18). The

extrapolated curve falls almost perfectly through the origin with a x-axis intercept corresponding

to less than 1 EO unit, indicating a strong phase separation between blocks compared with slight

intermixing observed with PS-PEO systems. Our data indicate that along the pseudoplateau, a









monomer of EO occupies 12.4 A+2, which is in good agreement with the value found for PS-PEO

systems.28,8

The monolayers were also transferred as Langmuir-Blodgett films on mica at various

surface pressures and analyzed by Atomic Force Microscopy (AFM) (Figure 4-21A), showing

different morphologies from analogous (PS-b-PEO) star copolymers.282,283

4.3.2 Reaction of the Polybutadiene Block at the Air/Water Interface in the Presence of
AIBN

Initially, photocleavage of AIBN under UV light was attempted to crosslink the

hydrophobic PB blocks of the (PB-b-PEO)3 COpolymer monolayers directly at the air/water

interface. For this purpose, 100 CIL of a solution of (PB200-b-PEO76)3 Star block copolymer in

chloroform at a concentration of C = 1 mg/mL and 100 CIL of a solution of AIBN in chloroform

at a concentration of C = 0.2 mg/mL were successively deposited on the water surface. The

monolayer was then compressed up to the desired surface pressure (20 mN/m) and the radical

polymerization reaction of the 1,2-PB double bonds initiated by the photo-induced

dimethylcyano radicals was carried out for 24 hours. At the end of the reaction, the surface

properties of the reacted material were investigated through isotherm and AFM studies. As

shown in Figure 4-19, a shift towards the low mean molecular area region was observed after

reacting the polybutadiene blocks. Furthermore, the progression of the reaction was followed by

IR analysis of an aliquot of the material removed directly from the water surface (Figure 4-20).

The disappearance of the peaks at 3100 cm-l and 1600 cml corresponding to the 1,2-PB double

bonds (=CH2 anti-symmetric stretch and alkenyl -HC=CH2 Stretch, respectively) confirmed

significant consumption of the pendant double bonds.

AFM characterization of the morphologies obtained before and after the reaction

confirmed the previous observations. Figure 4-21 shows images of monolayers transferred to









mica substrates at n = 20 mN/m at different reaction times. The images reveal submicron-sized

white circular domains that enlarge with reaction time, but remain separated. Due to the

hydrophilic nature of mica, we assume PEO transfers as the bottom layer, represented in the

images as the continuous dark phase, whereas PB occupies the top portion of the film

corresponding to the white higher elevation domains shown in Figure 4-21A. We suppose that the

bright domains correspond to crosslinked PB regions. The fraction of the surface occupied by the

bright domains increases with the reaction time until large portions of the surface is covered with

cross-linked and hydrophobic PB after 24 hours. However, the picture scanned at 40 Clm (Figure

4-21E) reveals that the bright domains remain isolated from each other and do not interconnect

across the film. The formation of these domains is consistent with a chain polymerization

occurring precisely at the spots of a radical initiation, which are also the nucleation spots. The

continuous PEO phase indicates that while some areas might have reacted, this strategy failed to

afford homogeneously cross-linked PB covering the entire surface.

4.3.3 Cross-linking with Hydrosilylated Polybutadiene Blocks at the Air/Water Interface

4.3.3.1 Application on polybutadiene homopolymer

To successfully demonstrate the viability of our method, we utilized linear polybutadiene

which is commercially available because of its world wild application as a commodity rubber

(Figure 4-22). Unsaturated polymers, especially diene polymers, are ideal for selective chemical

modification because of the technological importance associated with the parent materials. A

particularly interesting reaction involves the hydrosilylation of diene polymers to obtain silane-

modified rubber materials. Many papers and patents have appeared on the hydrosilylation of

polymers.300-312 In mOst cases, the hydrosilylated polydienes were used for the synthesis of

macromolecular complex architectures such as arborescent graft polybutadienes,313 multigraft

copolymers of polybutadiene and polystyrene,314 Or side-loop polybutadiene.315









We apply here the hydrosilylation reaction on the double bonds of polybutadiene chain

polymers. Triethoxysilane was used as the hydrosilylating agent in stoichiometric amount with

the total molar amount of double bonds in the polybutadiene chain (1,2- and 1,4-units), and

platinum(0)-divinyltetramethyldisiloxane complex (Karstedt catalyst) was used as the catalyst

(Figure 4-22). The reaction was heated up under argon for 24 hours at 80 OC in dry toluene (water

free environment). After workup, the hydrosilylated copolymer was analyzed by 1H NMR and

FTIR spectroscopy (Figures 4-23, 4-24, and 4-25).

The 1H NMR spectrum of the polybutadiene starting material was used to determine the

distribution of 1,2- and 1,4-units. The two protons of the pendant vinyl carbon in the 1,2-units

(=CH2) and the other hydrogens in the double bonds (-CH=CH- and -CH=CH2) having chemical

shifts of 4.9 ppm and 5.4 ppm, respectively, the polybutadiene turned out to be composed of 89

mole % of 1,2-PB units (Figure 4-23). The 1H NMR spectrum of the hydrosilylated

polybutadiene revealed a strong decrease in the intensity of the signal corresponding to the -

CH=CH2 (6 = 4.9 ppm) protons of the pendant double bonds. Furthermore, the appearance of

intense peaks at 6 = 1.2 ppm and 6 = 3.8 ppm corresponding respectively to the -Si-OCH2CH3

methyl protons and -Si-OCH2CH3 methylene protons indicated a high degree of conversion.

However, some pendant double bonds remained unreacted after hydrosilylation (Figure 4-24).

Based on the integration values of the signals at 6 = 4.9 ppm and 6 = 5.4 ppm, a conversion of 75

% of the 1,2-PB pendant double bonds was found, knowing that triethoxysilane reacts

predominantly with the 1,2-PB units as previously demonstrated.312

This result was confirmed by IR spectroscopy as shown in Figure 4-25, where the

absorbance peaks at 3100 cm-l and 1640 cm-l characteristic of -CH=CH2 double bonds (=CH2

anti-symmetric stretch and alkenyl -HC= CH2 Stretch, respectively) strongly decreased in









intensity after hydrosilylation. However, there are still unreacted pendant double bonds remaining

after reaction indicating less than 100% conversion.

After characterization of the PB68-CO-PB(Si(OEt)3)136 triethoxysilane-functionalized

polybutadiene, its cross-linking at the air/water interface by self-condensation of the

triethoxysilane pendant groups was studied.

Alkylalkoxysilanes have been widely used as reactive amphiphilic molecules at the

air/water interface.257,258,263,316-327 Our group has for instance investigated some of the

fundamental aspects of the chemical cross-linking of octadecyltrimethoxysilane (OTMS) and

octadecyltri ethoxy silane (OTES) molecules under acidic conditions at the air/water

interface.257,258,263,327

The mechanism of this 2D-acid-catalyzed cross-linking involves two different steps

(Figure 4-26): first, the hydrolysis of the ethoxy groups with the elimination of three ethanol

molecules to give the corresponding silanols, followed by condensation between the silanols

leading to the formation of a 2D-network.

The air/water interfacial cross-linking of the chemically modified PB(Si(OEt)3)

polybutadiene was first studied by recording isotherms after different reaction times (subphase

pH = 3.0 and x: = 0 mN/m) (Figure 4-27) with a barrier compression speed (100 mm/min) to

prevent additional cross-linking during monolayer compression. For comparison, the blue curve

illustrates the same polymer spread and rapidly compressed at pH = 3.0 before any significant

reaction could occur (Figure 4-27). As the reaction time is increased, the isotherms shift towards

the low mean molecular area region (loss of ethanol and water molecules during hydrolysis and

condensation, respectively). For reaction times longer than 10 hours, the isotherms essentially

overlapped which indicates completion of the cross-linking.










As shown in Figure 4-28 the monolayer static elastic modulus as calculated from the

expression (1).32

d7T
Es = -MMA x~ (1)
dMMA


significantly increases versus reaction time, indicating that the material becomes more

and more rigid as the extent of cross-linking is increased.

From these isotherms, the interfacial area occupied by one silane repeat unit before

reaction and its decrease during cross-linking were estimated (n: = 5 mN/m, pH = 3.0) and

compared with the values previously reported for OTES under similar experimental conditions.327

The MMA for the hydrosilylated polybutadiene decreases from 6300 A+2 (46 A+2/Silane repeat unit)

down to 3520 A+2 (26 A+2/Silane repeat unit), which corresponds to a decrease of approximately

AA = 20 A+2/Silane repeat unit. These values are in very good agreement with the ones reported

for OTES (46 A+2/mOlecule before cross-linking, 24 A+2/mOlecule after cross-linking, and AA = 22

A+2/mOlecule), and they clearly indicate that the extent of sol-gel cross-linking is not reduced

when starting from true polymeric chains compared to alkylalkoxysilane molecules.

The pH influence on the cross-linking reaction kinetics was shown by carrying out isobar

experiments at n = 10 mN/m and for different subphase pH values (Figure 4-29). As expected,

the MMA decreases faster for lower pH values. The isobar at pH = 7.0 shows a very slow creep

over time which demonstrates that the reaction is likely insignificant under neutral pH conditions.

For lower pH values (pH = 2.0 and 3.0), the curves overlap with the MMA leveling off after

about 7 hours indicating completion of the cross-linking reaction. The kinetics were consistent

with those reported for OTES and were slower compared to the results obtained for









OTMS,257,258,263,327 which is related to the slower elimination of larger alkoxy substituents during

the hydrolysis step.

Upon completion of the cross-linking reaction, the cross-linked material could be

subsequently manually removed from the interface with a spatula after its compression to a final

area of ca. 2 x 15 cm2 (Figure 4-30), leading to a film of approximately 50 monolayers thick. It

was self-supporting and gel-like, and could be collected as elongated sheets, which in turn could

be drawn into very long fibers at high elongation (Figure 4-30). As expected, it was insoluble in

common organic solvents such as chloroform or THF, making molecular weight analysis by SEC

impossible.

The evolution of the monolayer morphology during cross-linking was characterized by

AFM imaging of the LB film after transfer onto mica substrates (Figure 4-31, n: = 10 mN/m). As

a control experiment, it was first observed that under neutral pH conditions (pH = 7.0, no cross-

linking) the hydrosilylated polybutadiene forms a smooth and featureless monolayer (Figure 4-

31B) in opposition to the highly hydrophobic polybutadiene starting material which forms typical

rubbery continuous aggregates above the water surface (Figure 4-31A). After its hydrosilylation,

the polybutadiene becomes amphiphilic (hydrophobic backbone and hydrophilic triethoxysilane

side groups) and consequently surface active with the triethoxysilane pendant groups solvated

into the water subphase. This interfacial property of the hydrosilylated polybutadiene was also

shown in the isotherms where stable monolayers could be formed for surface pressures as high as

40 mN/m before collapsing (Figure 4-27). After 20 minutes of reaction (= 50 % extent of cross-

linking according to the isobar at pH = 3.0 and n: = 10 mN/m), the cross-linked material becomes

more hydrophobic and can be clearly observed in Figure 4-31C (bright areas) with an average

height of 1 nm as determined by cross-section analysis (Figure 4-31E). The cross-linked









polybutadiene has irregular borders and doesn't cover yet the entire mica surface. An AFM image

obtained after completion of the cross-linking reaction is shown in Figure 4-3 1D (10 hours, pH =

3.0, n: = 10 mN/m). Under these experimental conditions, most of the mica surface was covered

with a smooth and cross-linked monolayer. Therefore, we deliberately found an area with a crack

(that probably formed during film transfer) to clearly show the presence of the cross-linked

monolayer (bright area) on top of the mica substrate with a thickness that stays constant around 1

nm during cross-linking (Figure 4-31F).

4.3.3.2 Application on (PB-b-PEO)3 star block copolymer

Hydrosilylation of (PB-b-PEO)3 star block copolymers. We also applied the

hydrosilylation reaction on the polybutadiene segments of the (PB200-b-PEO326)3 Star block

copolymer. Triethoxysilane was used as the hydrosilylating agent in stoichiometric amount with

the total molar amount of double bonds in the polybutadiene block (1,2 and 1,4 units), and

platinum(0)-divinyltetramethyldisiloxane complex (Karstedt catalyst) was used as the catalyst

(Figure 4-32). The reaction was heated up under argon for 24 hours at 80 OC in dry toluene (water

free environment). After workup, the hydrosilylated copolymer was analyzed by 1H NMR and

FTIR spectroscopy (Figures 4-33 and 4-34).

Figure 4-33 shows the 1H NMR spectra of the (PB-b-PEO)3 Star block copolymer before

and after triethoxysilane hydrosilylation. The 1H NMR spectrum of the (PB-b-PEO)3 Starting

material was used to determine the distribution of 1,2- and 1,4-units in the polybutadiene block.

The two hydrogens of the pendant vinyl carbon in the 1,2-units (=CH2) and the other hydrogens

in the double bonds (-CH=CH- and -CH=CH2) having chemical shifts of 4.9 ppm and 5.4 ppm,

respectively, the PB block turned out to be composed of 75 mole % of 1,2-PB units. The 1H

NMR spectrum of the (PB(Si(OEt)3)-b-PEO)3 Star block copolymer revealed a strong decrease in

the intensity of the signal corresponding to the -CH=CH2 (6 = 4.9 ppm) protons of the pendant









1,2-double bonds. Furthermore, the fact that the signal of the -Si-OCH2CH3 methyl protons

increased in intensity (6 = 1.2 ppm) indicated that the reaction occurred with a high efficiency.

However, as shown in Figure 4-32, some pendant double bonds remain after hydrosilylation.

Based on the integration values of the signals at 6 = 4.9 ppm (-CH=CH2) and 6 = 0.5 ppm (-CH2-

Si-), a conversion of 85 % of the 1,2-PB pendant double bonds was found, knowing that

triethoxysilane reacts predominantly with the 1,2-PB units as previously demonstrated.312 This

result was confirmed by IR spectroscopy (Figure 4-34). The absorbance peak at 3100 cml

originating from -CH=CH2 double bonds (=CH2 anti-symmetric stretch) disappears after

hydrosilylation, but there are still remaining unreacted pendant double bonds as demonstrated by

the signal at 1640 cm-l (alkenyl -HC=CH2 Stretch) indicating less than 100% conversion.

Study of the cross-linking reaction at the air/water interface. The air/water interfacial

behavior of the chemically modified (PB(Si(OEt)3)-b-PEO)3 Star block copolymer was first

studied through isotherms at a subphase pH = 3.0 (Figure 4-35). Initially, the (PB(Si(OEt)3)-b-

PEO)3 Star block copolymer was spread on the water surface, and the cross-linking reaction (pH =

3.0) was carried out for 10 hours at very large surface areas where no surface pressure was

observed, then isotherms were recorded as shown in the lower curve of Figure 4-35. For

comparison, the top curve illustrates the same copolymer spread and rapidly compressed at pH =

3 before any significant reaction could occur. The isotherm of the non-silylated (PB-b-PEO)3

starting material forms the central curve of Figure 4-35. It is first observed that the isotherm of

the unreacted (PB(Si(OEt)3)-b-PEO)3 Star block copolymer is shifted to higher mean molecular

area region compared to the non-hydrosilylated starting material. The shift to larger areas is in

good agreement with the molecular weight increase of the star block copolymer after

hydrosilylation, with the hydrosilylated star block copolymer molecules occupying a larger









interfacial area. When the isotherm is carried out 10 hours after the monolayer formation at pH =

3.0 (complete cross-linking), a significant shift towards the low mean molecular area region was

observed (loss of ethanol and water molecules during hydrolysis and condensation, respectively)

indicating that the material is more compact. Another interesting feature is the lack of the

pseudoplateau at 10 mN/m in the unreacted silylated material, and its reappearance upon

crosslinking. This pseudoplateau corresponds to desorption of the poly(ethylene oxide) chains

from the surface to the aqueous phase below.298,299 We suppose that disappearance of the plateau

is due to increased mixing between the EO units and the significantly more hydrophilic silylated

units, while the crosslinking reaction would appear to induce demixing. The above interpretation

is corroborated by the length of the PEO pseudoplateau AA, which after cross-linking was 12,500

A+2 and compared well with that of the (PB-b-PEO)3 Starting material at 12,080 A+2

These above observations were confirmed by recording isotherms at pH = 3.0 after

different reaction times (Figure 4-36A). Fresh monolayers were spread for each experiment and

the barrier compression speed was set to 100 mm/min to prevent additional cross-linking during

monolayer compression. As the reaction proceeds, the isotherms shift to the low mean molecular

area region corresponding to a more compact cross-linked material with the PEO pseudoplateau

becoming more and more pronounced. Before the cross-linking starts, both the hydrosilylated PB

blocks and the PEO blocks are adsorbed at the interface with no PEO pseudoplateau. As the

reaction proceeds, we suppose the area occupied by the hydrosilylated PB decreases whereas the

fractional area occupied by the PEO stays the same. The reaction induces demixing of PEO

chains which explains the more pronounced PEO pseudoplateau. This observation was also

confirmed by plotting monolayer compressibility (K) versus mean molecular area for different

reaction times (Figure 4-36B). The compressibility (K) was calculated from the expression (2):









1 dA
K = -x (2)
A dH

where A is the mean molecular area and TIis the surface pressure. The development of

the pseudoplateau can be observed with the increase of the compressibility peak corresponding to

the PEO pseudoplateau transition (n: = 10 mN/m) that also shifts towards the low mean molecular

area region.

The pH influence on the cross-linking reaction kinetics is shown by the isobar


experiments carried out at n: = 5 mN/m and for different subphase pH values (Figure 4-37). The


low surface pressure was chosen to avoid the PEO phase transition. As expected, the MMA

decreases faster for lower pH values. The isobar at pH = 7.0 shows slow creep over time which

demonstrates that the reaction is likely insignificant at this pH. At lower pH values the mean

molecular areas overlap and stay constant after about 7 hours indicating completion of the cross-

linking reaction. As for the hydrosilylated PB, the cross-linking reaction kinetics were slower in

the case of triethoxysilane compared to the results obtained by Carino et al.263 foT

octadecyltrimethoxysilane (OTMS), which is consistent with the slower elimination of larger

alkoxy substituents.

Once the cross-linking reaction was complete, the cross-linked material could be removed

from the interface with a spatula after its compression to a final area of ca. 2 x 15 cm2 (Figure 4-

38), approximately 50 monolayers thick. Unlike the (PB-b-PEO)3 Star block copolymer, this

material was self-supporting and gel-like and could be collected as elongated elastic sheets,

which in turn could be drawn into very long fibers at high elongation (Figure 4-38). As expected,

it was insoluble in common organic solvents such as chloroform and THF, making molecular

weight analysis by SEC impossible. It should be noted that this behavior was in sharp contrast to









the fi1ms formed from AIBN, which could not be pulled from the surface as free standing fi1ms or

fibers under any conditions attempted.

Surface pressure influence on the morphology of the cross-linked material. The LB

fi1m morphologies obtained after cross-linking at different surface pressures were characterized

by AFM after monolayer transfer to mica substrates (Figure 4-39). It is assumed that the

monolayer morphologies are not modified during LB fi1m formation as indicated by the transfer

ratio values close to unity (T.R. = (Area of the surface film transferred) / (Area of the mica


substrate)). As a control experiment, it was first observed that at n: = 5 mN/m and pH = 7.0 (no


cross-linking reaction), a smooth featureless monolayer with no phase separation between the

hydrosilylated PB blocks and the PEO blocks is obtained (Figure 4-39A). After the

hydrosilylation reaction, the PB block becomes more hydrophilic because of the triethoxysilane

pendant groups and therefore is adsorbed at the air/water interface just like the PEO block. This

interfacial property of the hydrosilylated PB block was also demonstrated with hydrosilylated PB

homopolymers that formed stable monolayers for surface pressures as high as 40 mN/m (Figure

4-27). Such behavior differs significantly from the PB block of the (PB-b-PEO)3 Star block

copolymer which is much more hydrophobic and aggregates above the water surface. When LB

transferred monolayers of the silylated block copolymer reacted under isobaric conditions for 10


hours at n = 2 mN/m and pH 3.0 were examined by AFM (Figure 4-39B) a clear phase


separation between the cross-linked material (yellow areas) and the poly(ethylene oxide) chains

(dark areas) could be observed with the average height of the cross-linked monolayer being about

2 nm. However it is only at surface pressures of about 6 mN/m and above that true PEO pores

can be seen within the PB network (Figure 4-39D). As the surface pressure increases, the average









PEO pore size decreases (Figure 4-39D-G) to reach a morphology with very small PEO domains

trapped within a 2D cross-linked PB network (n: = 9 mN/m; Figure 4-39G). For higher surface

pressures such as 15 mN/m (Figure 4-39H), the cross-linked material covers the entire surface

with the PEO "pores" barely visible. This is in good agreement with the observation that PEO

chains are pushed under the water surface at 10 mN/m.

The topography was further investigated by section analysis of the AFM images (Figures

4-40A and B). The height signal amplitude is significantly smaller for the image scanned for a

surface pressure of 15 mN/m since the PEO pores are barely visible. The average sizes of the

PEO pores obtained for different surface pressures were roughly determined from the analysis of

the power spectral density (PSD) (Figures 4-40C and D) of the surface morphology measured by

AFM.329 The maximum of the large peak in the PSDs corresponds to the average distance

between nearest neighbor domains for non-porous material and the average size of the PEO pores

for a porous material (Figure 4-40D). We observe that for a surface pressure of 5 mN/m, at which

the cross-linked material is not "porous", the approximate distance between two PB cross-linked

domains is =180 nm. This characteristic pore size decreases with surface pressure applied during

the cross-linking reaction from =130 nm for n: = 6 mN/m until it reaches a value in the range =40

nm for n: = 9 mN/m (Figure 4-40C). The curves for surface pressures of 7 and 8 mN/m were not

included for easier visualization, but the average PEO "pore" sizes for these surface pressure

were found to be equal to 46 and 42 nm, respectively. For higher surface pressure such as 15

mN/m, no maximum is observed for the PSD curve. This is in agreement with the fact that no

PEO "pores" can be seen at this surface pressure as shown by the AFM picture (Figure 4-39H).

From these AFM images and the spectral power density study, it can be concluded that with

hydrosilylated PB blocks, the cross-linking reaction is more homogeneous than with AIBN,









allowing the formation of a two-dimensional gel with controlled PEO "pore" size by simply

changing the polymerization surface pressure. The silane chemistry proceeds by a step growth

mechanism which will favour homogeneous coupling over the entire surface in contrast to the

chain growth mechanism of AIBN which would favour nucleation spots.

An experiment to illustrate retention of the morphology after cross-linking was attempted.

The (PB(Si(OEt)3)-b-PEO)3 mOnolayer was cross-linked at constant surface pressure n: = 9 mN/m

and pH = 3.0 (t = 10 hrs), and then the cross-linked monolayer was transferred (Figure 4-41). A

second transfer of the same cross-linked material was performed after the expansion of the

system to x = 2 mN/m. As shown by the images in Figure 4-41, the same morphology is observed

before (n: = 9 mN/m; pH = 3.0, t = 10h) and after expansion (n: = 2 mN/m; pH = 3.0) with only a

slight increase of the PEO pore size after monolayer expansion.

A final experiment was attempted to prove that for high surface pressures, the PEO chains

are irreversibly displaced to the aqueous phase underneath the cross-linked PB network. After

cross-linking the monolayer (t = 10 hrs, pH = 3.0) at 20 mN/m (surface pressure above PEO

aqueous dissolution), the barriers were expanded and the isotherm of the resulting cross-linked

monolayer was recorded as shown in Figure 4-42 (Blue curve). The PEO pseudoplateau is no

longer present which indicates that the PEO chains were irreversibly positioned underneath the

PB cross-linked network and could not readsorb at the interface during monolayer expansion. A

control experiment was carried out by recording the isotherm of the monolayer cross-linked at 5

mN/m, that is below the surface pressure corresponding to the PEO blocks aqueous dissolution

(Figure 4-42, red curve). As expected, the PEO pseudoplateau is still present (even after several

hysteresis cycles), which confirms that it is possible for high surface pressures (n: > 10 mN/m) to









freeze the "thicker" conformation (PEO sublayer underneath a PB network) of the cross-linked

material.

4.4 Conclusion

The main obj ective of this study was to propose a new and general method to synthesize a

novel two-dimensional polymeric nanomaterial consisting of a continuous cross-linked

polybutadiene network containing poly(ethylene oxide) pores of controlled sizes. To reach that

goal, novel (PB(Si(OEt)3)-b-PEO)3 Star block copolymers were synthesized by hydrosilylating

the PB pendant double bonds of (PB-b-PEO)3 Star block copolymers with triethoxysilane. The

hydrolysis and condensation of the triethoxysilane pendant groups of the (PB(Si(OEt)3)-b-PEO)3

star block copolymer under acidic conditions allowed us to easily crosslink the polybutadiene

block directly at the air/water interface without any additives or reagents. This demonstrated the

improved efficiency of this method compared to the radical polymerization in the presence of

AIBN to get a homogeneously cross-linked material with controlled and Eixed morphologies.

This strategy permits the control of the PEO pore size by simply adjusting the surface pressure

during the cross-linking reaction as shown by AFM imaging of the LB fi1ms.

The characterization of these 2D amphiphilic cross-linked materials are currently under

investigation (permeability, small angle scattering, and 2D viscometry) to understand the benefits

provided by 2D self-assembly at the air/water interface over conventional solution self-adsorption

and other processes. At stake is the possibility to use 2D self-organization as a means to construct

materials with anisotropic structures, to reproducibly engineer such structures, and to target

defined functions with these materials. In addition, such copolymer silanes monolayer could be

easily transferred and grafted through covalent bonds to inorganic surfaces (glass support such as

silicon wafer) for polymer/inorganic composite synthesis. Work is also in progress to introduce

triethoxysilane groups, and other metal alkoxides on other polydiene block copolymers of more









complex architectures such as triblock copolymers with the aim toward the stabilization of other


original 2D and 3D morphologies.


Figure 4-1.


Direct visualization of the 1% unreacted (A) and 0.05% cross-linked (B) wormlike
micelles of PB45-b-PEOss diblock copolymer by cryotransmission electron
microscopy. Sketches illustrate the local structure of pristine and cross-linked PB
cores. Use of a lower concentration in (B) was necessitated by the gel-like character
of the 1% cross-linked solution.


Figure 4-2.


Formation and osmotic deflation of PB46-b-PEO26 diblock
without (A, B) or with (C) cross-linking between the
butadiene.


copolymer, vesicles either
hydrophobic segments of


~Orm


r
.-~..,.


3
i~15









A j '"'








Langmuir-Blodgett Transfer





support




Molecular x n
pore


CH CHI 2H


HgO2CCF3
n r ~HgO2CCF3Wae HgO2CCF3








aopst macop rao s srutpoport


Water


X =HgO2CCF3, C(=0)NHCH2CH2SSCH3,
C(NH2)=NOH, C(=S)N(CH3 2, or CH=CH2
R = C2H5, n-C4H9, n-C8H17, or n-C16H33


Figure 4-3. (A) Representation of the concept of a two-dimensional network of molecular pores,
i.e., "perforated monolayers". (B) Stabilization of the resulting assembly via
polymerization before and after transfer to a macroporous substrate.


~~Br




CH~B


p~


A quasilinear coupler (a, p-xylylene dibromide), a cross-shaped monomer (b,
lanthanum sandwich complex of tetrapyridylporphyrin), an idealized structure (c),
and an STM image (d) of a square grid.


Figure 4-4.








OBr


5


Rx M IR
N N


R = O-CH-(CCH2)19CH3
COOH


R3 = C22H45


R2 OBr
(CH2)19CH3

Figure 4-5. (a) Amphiphilic porphyrins Pi and P2. Pi: R = R1 (M = H2, Cu); P2: R = R2 (M = H2,
Cu, Fe). (b) Amphiphilic porphyrazine P3 (M = Cu).


i +3HO
HOSI O 3~O
H+/ \HO 3C\


A)

1 Hydrolysis


HOSI \OH -HZO
HO


HO/ S O/ S OH
HO HO


HO SI \OH
OH


2 Condensation


~
.?F q!: ;Y
Itir IlilC:llll 41FI :~DV


Figure 4-6. (A) General reactions involved in the polymerization of alkoxysilanes; (B) Pressure-
area isotherms obtained for pH = 3.5 at 25 OC after different reaction times; (C)
Gelation of the OTMS monolayer as observed from Brewster angle micrographs.




























NH N NIP

370 200/ O 43%



Figure 4-7. Molecular structure of the lipopolymer polymerized by exposure to UV light.



34 PB,,-b-PEOxys),

(PB,,-B-PEOS,)
28-
E *'. (PB,,-b-PE01as)d
24 -I (P,,Br--PEO,,),

a 20-
18-

14
1 Cl







1000 10000 100000

Mean Molecular Ar ea (ia')



Figure 4-8. Surface Pressure-Area per polymer molecule isotherms at 298K for (PB76-b-PE0n)4
star block copolymers (n = 57, 137, 444 and 1725).






















12-1--~-21- 1


-5c i8 I
3A A
I / pancake_

0 100000 200000 300000 400000 500000

Mean Molecular Area (A2)


Figure 4-9. Isotherm of (PB76-b-PEO444)4 depicting how measurements of molecular area for the
three principal regions are obtained.


2.5x10 -


2.0 x10 -






1.0 x10 -


5.0 x1 04


0 1000 2000 3000 4000 5000 6000 7000

Total nurnber of ethylene oxide units


Figure 4-10. Linear dependence of A, on the total number of ethylene oxide units.












1.2x106


1.0 x106









( 00 20 00 400 50 00 70
Toalnmbrofehyen xieunt


Figure ~ 4-1 Lna eedec fA peuolta nth oa ube fehlneoieuis



























I I I I


(PB76-b-PEO ,)4
H = 5 mN/m
Cycle
Order
5--1


(PB76-b-PEO ,,)
H= 5 mN/m
Cycle
Order
5- 1


5000 106000
Mean Molecular Area (A2)


15000


2x105 3x O' 4x O'

Mean Molecular area (A2


5x 05


(PB76-b-PEO,),
n= 10mN/m
Cycle
Order
5--1


^ 10-
z ,.



2


E
z
E
a,
L
v,
B) v,
a
a,
o
m

v,


(PB76-b-PEO1725 4
H= 10mN/m
Cycle
Order


20b00 4d000' 6000 80b00 10~000' 126000

Mean Molecular Area (A2)


1x105 2x105 3x105 4x105 5x105

Mean Molecular Area (A2


SFirst cycle
SSecond cycle
SThird cycle
SFourth cycle
-eFifth cycle


(PB76-b-PEO1725 4
II= 15mN/m


16

12











-2-
C


E




C)




m


5+-1


1000 2000 3000 4000 5000

MC811 MOlecular Area (A2)


O 2000 4000 6000 8000 10000 12000

Mean Molecular Area (A2)


Figure 4-12.


Compression/expansion curves for two different samples of PB4-b-PEO4 Star block
copolymers ((PB76-b-PE057)4 and (PB76-b-PE057)4) at (A) 5 mN.m l, (B) 10mN.ml
and (C) 15mN.ml











2.5


1-


0.5-



0 2 4 6 8 10 12 14 16

Su rface Pressu re (m N/m)



Figure 4-13. Evolution of transfer ratio with the surface pressure in the case of (PB76-b-PE0l725)4
star block copolymer sample.








A) B) C)
5.0 nm F 0 nm 10.0 nm







0.0 nm 1 0.0 nm 00n

n = 2 mN/m n = 4 mN/m n = 6 mN/m



--- F 0 nm 1.0 nm 5.0O nm





I 3.0nm I 2. 0 nm ~ ZC~~~F 2.5 nm

0.0 nm y 0.0 nm -0.0 nm

n: = 8 mN/m n: = 9 mN/m n: = 10 mN/m


G) H)
-71nm -71 nm





1 3 .5 n m ~ ~ SC4 3 5 n m

0.0 nm -l' C~~LleS 0.0 nm

n = 11 mN/m n = 15 mN/m


I) J)
6.5 nm ~ C 5.0 nm







-0.0 nm IBfi l 0.0 nm

n: = 20 mN/m n; = 30 mN/m



Figure 4-14. AFM tapping mode amplitude images of the (PB76-b-PE0l725)4 (A, B, C, D, E, F, G
and H) and (PB76-b-PE057)4 (I and J) star block copolymers transferred to a mica
plate support at various surface pressures. The films are scanned at a scan rate of
1Hz with a scale of 2 x 2 Cpm (A, B, C, D, E and I) and 5 x 5 Clm (F, G, H and J).














180-

160-

c 140-

E 120-





S 60-

40-


20

0 2 4 6 8 10
Pressure (mNlm)



Figure 4-15. Dependence of the number of molecules per domain on the surface pressure in the
case of the (PB76-b-PE0l725)4 Star block copolymer sample. The general trend shows
that as pressure increases, more molecules aggregate (dramatic increase from TI = 4
mN/m) to form the observed circular PB microdomains.










PB domains
)8( PEO chains


PEO chamns
in extension




\/L PEO


n] = 2 mN/m


Water subphase


n = 8 mN/m


PB elongated
/ stripes


7C = 15 mN/m


Figure 4-16. Model proposed to explain the formation of a network of elongated stripes. (a) Long
PEO branches staying at the water surface as globules create a weak separation
between the PB microdomains. (b) As the surface pressure increases, the PEO
blocks are pushed to the maximum hydration by a total extension of their chains on
the surface of water. (c) Upon further compression, the PEO chains, too long to be
totally submerge into the water subphase, shift to allow the PB microdomains to
aggregate through only one point of contact to give elongated stripes.












- (PB ,-b-PEO ,),

- (PB ,-b-PEO ,),


3-


30


E 25

S20


a


1000


10000 100000


Mean Molecular Area (A2)



Figure 4-17. Surface Pressure-Area per polymer molecule isotherms for (PB200-b-PE0n)3 Star
block copolymers (n = 76, 326, 970, and 2182).


9x10 -









o ,, ,, ,






I 1000 2000 3000 4000 5000 6000 7000
Total Number of
ethylene oxide units


a


o

a
ur


Figure 4-18. Linear dependence of AApseudoplateau On the total number of ethylene oxide units.


III


IIRQ


























10000 20000 30000
Mean Molecular Area (iM)


40000


Figure 4-19. Surface Pressure-Area isotherms for (PB200-b-PEO76)3 Star block copolymer before
(-) and after (-) cross-linking in the presence of AIBN under UV light (x: = 20
mN/m) .


4000


3500 3000 2500 2000 1500 1000 500

Wavenumber (c~m )


Figure 4-20. IR spectra of (PB200-b-PEO76)3 before (-) and after (-)
presence of AIBN under UV light.


cross-linking in the



















t = Oh t = 12h
C) D)





i 0.0 nm 0nr


E)
3.0 n


1. 5 nm


0.0 n


t = 24h


Figure 4-21. AFM topographic images of the (PB200-b-PEO76)3 Star block copolymer transferred
to mica substrates (n: = 20 mN/m) before (A) and after cross-linking (B, C, D, and
E) at different reaction times. The films are scanned with a scale of 10 x 10 Cpm (A,
B, C, and D) and 40 x 40 Clm (E).









H + HSi(OCH2CH3 3
22\ 1182




Pt
Toluene / 80 oC /24h





22\ 146\ 1136




H3CH2CO SiOCH2CH3
OCH2CH3


Figure 4-22. Hydrosilylation of the pendant double bonds of the PB homopolymer.


a e


C HCX
a ~CH,




c and d


CHClz


b in b L
o eo h,


6 (pp m)

Figure 4-23. 1H NMR spectrum (CDCl3 ; 300MHz) of the commercial linear polybutadiene.









da f d

CC
H2 H H2
b h

HCH CO' IOCH2CH3
OCH2CH3
f and g







I'CI






7.0 6.0 5.0 4.0 3.0 2.0 1.0

8 (pp m)


Figure 4-24. 1H NMR spectrum (CDCl3 ; 300MHz) of the hydrosilylated polybutadiene.


SPB-co-PB(Si(O~tj))

1 PB homopolymer



S 0.7
07068 -



S0.5 -
S:-CH=CH, -CH=CH,

0.3
0.2

0.1 |


3900 3600 3300 3000 2700 2400 2100 1800 1600 1200 900 600

Wavenu mber (cm-)
Figure 4-25. IR spectra of the polybutadiene before and after hydrosilylation.













H
Si
HO OH
HO


O iO










OH


+3HO
-3EtOH


Hydrolysis


HO


-HO HO O H
HO HO


Condensation


: Polybutadiene backbone



Figure 4-26. Cross-linking reaction involving hydrolysis and condensation of the triethoxysilane
groups of the polybutadiene backbone.


- t= 600 rnn
-t = 90 rnn
-t = 60 mnu
t = 40 rnn
-t = 20 mnn
-t = rnn


0 2000 4000 6000 8000


Mean Molecular Area (~2)



Figure 4-27. Surface pressure-Mean Molecular Area isotherms of the hydrosilylated
polybutadiene carried out after different reaction times (subphase pH = 3.0).


10000








70 600 min
90 min









40




0 10 20 30 40 50
Surface Pressure (mN.m l)


Figure 4-28. Static elastic modulus-surface pressure curves of the hydrosilylated polybutadiene at
different reaction times (subphase pH = 3.0).


pH = 7.0


m =



E 2


pH = 5.5


pH = 3.0


0.66


0.49


0 100 200 300 400 500


600


Time (min)
Figure 4-29. Mean Molecular Area-Time isobars of the hydrosilylated polybutadiene for various
subphase pH values (n: = 10 mN/m).

































Figure 4-30. (A and B) Removal of the cross-linked homopolymer from
surface. The white material easily comes off the interface
Picture of the long cross-linked fiber dried under vaccum.


the Langmuir trough
using a spatula. (C)


10.0 nr



15.0 nr


IS.5 nn

0.0 nn


0.0 nm


sF)


$- E)
2---_-i~---


Figure 4-31. AFM topographic images of the LB films transferred onto mica substrates at n: = 10
mN/m: the commercial polybutadiene (A) and the hydrosilylated polybutadiene at
pH = 7.0 (B; t = 0 h) and 3.0 for different reaction times (C ; t = 20 min and D; t =
10 h). (E and F) Cross-section analysis of the images C and D. The images are 7 x 7
Cpm2 (A) and 50 x 50 Cpm2 (B, C, and D).


I ~3. nm


-0.0 nm













+ HSi(OCH2CH3)3


P O[(CH2=CH(Mc),Si]aO
Toluene / 800C /24h


EtO \ 'OEt
Oft


Figure 4-32. Hydrosilylation of the pendant double bonds of the (PB-b-PEO)3 Star block
copolymer.





























































h)


7.0~ '6.0' '5.0' '4.0~ '3.0' ~ 2.0' 1. '0.0

5 (ppm)



Figure 4-33. 1H NMR spectra (CDCl3 ; 300MHz) of (PB200-b-PEO326)3 Star copolymer and the
corresponding hydrosilylated (PB78-co-PB(Si(OEt)3)122-b-PEO326)3 Star block
copolymer.


f d


c CH2 h
H H, ~ Hb
I c


I I ~ I I I ~


f


5.0 4.0


2.0 1.0


7.0 6.0


~O hi
B~







- (PB-b-PEO)3
- (PB(Si(OEt),)-b-PEO),


3900 3600 3300 3000 2700 2400 2100 1800 1500 1200 900


600


Wavenumber (cm-l)

Figure 4-34. IR spectra of the (PB200-b-PEO326)3 Star block copolymer and the corresponding
hydrosilylated (PB s-co-PB(Si(OEt)3)122-b-PEO326)3 Star block copolymer.


40- 0-

E 3n pH = 3.0
t = 10 his



20 -



250 *--l 1-

U 400 000100



Mean Molecular Area (A2)


Figure 4-35.


Surface Pressure-Area isotherms for (PB200-b-PEO326)3 Star block copolymer and the
corresponding hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star block copolymer before
(pH = 3.0, t = Oh) and after (pH = 3.0, t = 10h) cross-linking.









t, =0 min
E` 3o- -~, t, = 20 min
t, = 30 min
E 25- -~~ t, = 40 min
t, =60 min
--20--t= 100 min
A) v- 600 min
a15-







0 20000 40000 60000 80000 100000

Mean Molecular Area (A2)


0.4
t, = 600 min
S0.35- t, = 100 min
E t 60 min
E0.3 t, = 40 min
0.25 j- t, = 30 min
>I t 20 min
B) 0.-1-t .=O min



0.



5000 10000 15000 20000 25000 30000
Mean Mnolecular Area (A2)


Figure 4-36. Surface pressure-Area isotherms (A) and Compressibility-Area curves (B) for the
hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star block copolymer carried out at different
reaction times (sub phase pH = 3.0).
















C11
m



NL
m

Eu
LQ1
0O


0 100 200 300 400 500 600 700

Time Imin)


Figure 4-37. Isobars of the hydrosilylated
various subphase pH values (: =


(PB(Si(OEt)3)-b-PEO)3 Star block copolymer for
5 mN/m).


Figure 4-38. Removal of the cross-linked (PB(Si(OEt)3)-b-PEO)3 Star copolymer from the
Langmuir trough surface. The dark yellow material easily comes off the subphase
using a spatula.


~llr
















-0.0 nmn


n; = 5 mN/m
pH = 7.0


n] = 2 mN/m
pH = 3.0
E)


n] = 5 mN/m
pH = 3.0
F)


n; = 6 mN/m
pH = 3.0


n; = 7 mN/m
pH = 3.0


n: = 8 mN/m
pH = 3.0


500 nm


n: = 9 mN/m
pH = 3.0


n] = 15 mN/m
pH = 3.0


Figure 4-39. AFM topographic images of the (PB(Si(OEt)3)-b-PEO)3 Star block copolymer LB
films transferred to mica substrates at subphase pH = 7.0 (A; t = 0 h) and 3.0 for
different surface pressures (B, C, D, E, F, G and H; t = 10 h). The films are scanned
with a scale of 2 x 2 Cpm.





















Surfece pressure (mNlm)
x = 6 mNim
16 x 9mNim
141 x-15rNam






Wavelength (pm)


b


E
r
m
c> E


~L=b mnim


D, 5


~ rlrihh "i I,
5'


n = 15 mN/m


Figure 4-40. (A and B) AFM section analysis of the images of the (PB(Si(OEt)3)-b-PEO)3 Star
block copolymer LB films transferred to mica substrates at subphase pH 3.0 for
different surface pressures (t = 10 h). The films are scanned with a scale of 2 x 2
Clm. (C) PEO pore size-Surface pressure curve for the hydrosilylated (PB(Si(OEt)3)-
b-PEO)3 Star block copolymer after cross-linking at different surface pressures
(subphase pH = 3.0). (D) PSD curves obtained from AFM images of (PB(Si(OEt)3)-
b-PEO)3 Star block copolymer LB films.


13.0


1. 5 nm



0.0 nm


Transferred at
n: = 9 mN/m


Transferred at
n = 2 mN/m


Figure 4-41. AFM topographic images of the (PB(Si(OEt)3)-b-PEO)3 Star block copolymer LB
films transferred to mica substrates at subphase pH = 3.0 (t = 10 h) before (n: = 9
mN/m) and after (n: = 2 mN/m) expansion of the monolayer.


, 1,.


1) Expansion



2) Transfer at
n = 2 mN/m
0.0 m




































I ~I
20000 40000 60000 80000 100000

Mean Molecular Area (A2)


= 20 mN/m
40 -


S30-

25-

20 -0

S15 -




( 5


*Hydro~silylated PB
as' PEO




n: = 20 mN/m X; = 5 mN/mn

aCrosslinking Crosslinking



Ex ansion OCompressi on I = 5mNlm
Expansion Compression



~---~____--


7C = 5 mN/m


Figure 4-42.


Surface Pressure-Area isotherms for the hydrosilylated (PB(Si(OEt)3)-b-PEO)3 Star
block copolymer cross-linked at subphase pH 3.0 (t = 10 hrs) for two different
surface pressures (n: = 5 and 20 mN/m).


Table 4-1. Measurements obtained from isotherm experiments of (PB-b-PEO)4 amphiphilic star
block copolymers.


Ao/number of
Ao/molecule Ao/PB unit AA pseudhe lateaP"~ U 2laa~P n
(nm ) (nm ) 2(Hm )
(nm )
29.6 0.097 7.4 35.23 109.77


Sample


(PB76-b-PE0s?)4
(PB76-b-PE0137)4
(PB76-b-PEO444)4
(PB76-b-PE0l725)4


32.66
37.2
36.01


0.107
0.122
0.118


81.22
254.33
1055.07


254.38
904.87
2489.23


8.16
9.3
9










Table 4-2. Characteristics of LB film experiments.


Surface
pressure
(mN/m)
2
4
6
8
9
10
11


Mean molecular
area (MMA)


217038
173599
146140
119154
96736
10843
3749
1991
1169


Transfer ratio>


1.029
1.06
0.943
1.05
2.089
1.937
2.12
1.916
1.84


Polymer


Run


(PB76-b-PE0l725)4


(PB76-b-PE0s?)4


a) (Area of the surface film)/(Area of the pulled mica substrate).



Table 4-3. AFM characteristics of (PB-b-PEO)4 four-arm star copolymers.


Average
diameter of
PB domains
(nm) (A 7)
61
67
71
132
84
C)
C)
C)
54
550


Number of
molecules per
domain
(A 10)

14

101
186
22




900
87836


Surface
pressure
(mN/m)

2
4
6
8
9
10
11
15
20
30


Vertical
height
(nm) (A 1)

2.234
3.413
4.729
4.837
4.526
4.9
5.09
5.181
2.082
5.282


Number of
domains
(A 50)

445
170
27
18
193
C)
C)
C)
380
38


PB coverage
a
area
(%) (A 10)

32
15
3
6
9
C)
C)
C)
22
36


Run


A
B
C
D
E
F
G
H
F
G


a) Coverage area (xnr2)(Number of domains)/Scan area. b) Molecules/domain Scan
area/[(Number of domains)(Mean molecular area)]. c) At these surface pressures, films are in a
multilayer regime.










Table 4-4. Data for (PB-b-PEO)3 and (PB(Si(OEt)3)-b-PEO)3 Star block copolymers.

Mn~a) Mnb) Mne) 1,2-PB b)
Run Mw/M a) Code
(SEC) ( H NMR) (theo) n o)

1 45900 42500 40500 1.2 75 (PB200-b-PEO76)3
2 56000 75500 77500 1.15 75 (PB200-b-PEO326)3
3 58000 160500 164500 1.2 75 (PB200-b-PEO970)3
4 74000 320500 323000 1.2 75 (PB200-b-PEO2182)3

5 135500 30 (PB72-CO-PB(Si(OEt)3)128
-b-PEO326)3
a) Apparent molecular weights determined by SEC in THF using a polystyrene calibration.
b) Estimated by 1H NMR analysis.
C)M~n,th = MButadiene X ([Butadiene]/[-PhLi]) x 3 + MEo x ([EO]/[(PB-OH)3 -









CHAPTER 5
PLURICARBANIONIC MACROINITIATORS BY A LITHIUM/HALIDE EXCHANGE
REACTION: APPLICATION TO ASYMMETRIC AND MIKTOARM STAR AND
DENDRIMER-LIKE POLYMER SYNTHESIS

5.1 Introduction and Literature Overview

In the past five decades, a lot of efforts was put on the synthesis of more and more

complex macromolecular structures, because of their unique and particular properties as well as

their usefulness and potential, starting from the most simple one, star polymers,33 including

asymmetric and "miktoarm" star polymers with only one junction point, until the synthesis of the

most complex ones, such as regular dendnimers,33~3 comb-type,33 graft,333 dendritic

macromolecules (dendrigrafts,3 13,338-341 COmb-burst polymers,342 pOlymers with dendritic

branching,343-345 and dendrimer-like polymers341,346,347) and hyperbranched polymers.331,348-351

The chemists are still trying to get easier strategies for the synthesis of such complex

architectures. As it is well-known, the strategy usually used for the synthesis of AA'2 and AB2

three-arm asymmetric and miktoarm star polymers consists first in the introduction of a

branching point at the linear chain end to obtain thus two geminal initiating or electrophilic sites

for the growth of two new polymer chains (divergent method) or for the coupling reaction of two

"living" chains (convergent method), respectively. This is also a model used for the preparation

of dendrimer-like polymers: the reiteration of the aforementioned sequence of reactions allowed

to derive dendrimer-like polymers of different generation.

5.1.1 Asymmetric and "Miktoarm" Star Polymers

Asymmetric stars are a special class of stars (see p. 56 for regular stars) that is

characterized by an asymmetry factor compared to the classical symmetric structures previously

described (Chapter 3). The following parameters have been considered as asymmetry factors

(Figure 5-1):









Molecular Weight Asymmetry. All the arms of the star are identical in chemical nature,
but they have different molecular weights.

Functional Group Asymmetry. The arms are of the same chemical nature and have the
same molecular weight, but they have different end groups.

Topological Asymmetry. The arms of the star are block copolymers that may have the
same molecular weight and composition but differ with respect to the polymeric block
that is covalently attached to the core of the star.

Another important class of stars is the miktoarm, or heteroarm star polymers. The term

"miktoarm" or heteroarm star polymer refers to stars consisting of chemically different arms. In

the past decade considerable effort has been made toward the synthesis of miktoarm stars, when

it was realized that these structures can exhibit very interesting properties.336,352,353 The most

common examples of miktoarm stars are the AB2, A3, A2B2, A,,B,, (n > 2) and ABC types.

Other less common structures, like the ABCD, ABS, and AB2C2 are HOw also available.

In our case, we will be especially interested in AA'2 and AB2 three-arm asymmetric and

miktoarm star polymers. There are two different methods to prepare such AA'2 and AB2 pOlymer

structures by anionic polymerization: the chlorosilane method and the diphenylethylene

derivative method.141 The chlorosilane method was initially reported by Fetters354 and was later

developed by Hadjichristidis, Mays, and collaborators.139,336,353,355 Chlorosilanes are used as

linking agents for the stepwise replacement of the chlorine atoms by the polymer chains (Figure

5-2). This method was first applied to the synthesis of asymmetric polystyrene (PS),

polybutadiene (PB), and polyisoprene (PI) stars having two arms of equal molecular weights and

a third one having molecular weight either half or twice that of the identical arms.354,356

The procedure, given in Figure 5-2, involves the reaction of the living arm PSALi with a

10-fold excess of methyltrichlorosilane for the preparation of the methyldichlorosilane end-

capped PSA. This is the crucial step of the synthesis, keeping in mind that there is a possibility to









form the coupled byproduct, i.e., the two-arm star with only one remaining Si-Cl group. This is

avoided by using a large excess of the linking agent, adding the linking agent solution to a dilute

living polymer solution under vigorous stirring and performing the linking reaction at low

temperatures (5 OC). Under these conditions, no coupled byproduct was observed.

After the removal of the silane excess, the two remaining Si-Cl bonds of the

methyldichlorosilane end-capped PSA Tar Were reacted with a small excess of living PSBLi

chains. The PSBLi chains were end-capped with a few units of butadiene to facilitate the

completion of the linking reaction.

The same strategy was also used for the preparation of miktoarm star copolymers. A near

monodisperse miktoarm star copolymer of the AB2 type was first reported by Mays,355 A being

PS and B PI. The synthetic method adopted was similar to the one applied by Fetters354 for the

synthesis of the asymmetric PS and PB stars. The living PS chains were reacted with an excess of

methyltrichlorosilane to produce the monosubstituted macromolecular linking agent. The steric

hindrance of the living polystyryllithium and the excess of the silane led to the absence of any

coupled byproduct. The silane excess was removed and then a slight excess of the living PI

chains was added to produce the miktoarm star PS(PI)2. Excess PI was then removed by

fractionation. This method was later extended by Mays, Fetters and Hadjichristidis to the

synthesis of the AB2 Stars, where A and B were all possible combinations of PS, PI, PB and

PDMS. 109,113,355,357-360

A different approach was adopted by Eisenberg and colleagueS361 for the synthesis of

P2VP-b-(PS)2 miktoarm stars, where P2VP is poly(2-vinylpyridine). Methyldichlorosilane

(CH3SiCl2H) was used as linking agent to produce the two-arm PS star. Living P2VP was reacted

with allyl bromide to give an end-functionalized polymer carrying a terminal vinyl group. In the

last step a hydrosilylation reaction of the Si-H group of the two-arm star with the end-double









bond of the P2VP chain produced the desired structure (Figure 5-3). Rather high molecular

weight distributions (2y/2, = 1.33-1.50) were obtained, probably due to incomplete

hydrosilylation reaction. High molecular weight P2VP, end-capped with vinyl groups

(macromonomer), were used to avoid the steric hindrance effects and facilitate the

hydrosilylation reaction. Consequently, the method suffers limitations and cannot be used in

general for the synthesis of miktoarm stars.

On the other hand, the diphenylethylene derivative method is based on the use of 1,1-

diphenylethylene derivatives that are non-homopolymerizable monomers. A rich chemistry was

developed, leading to the formation of several types of asymmetric stars. The groups of Quirk

and Tungl5,17,18,21,208,362 reacted living PS chains with either 1,3-bis(1 -phenylethenyl) benzene

(MDDPE), or 1,4-bis(1 -phenylethenyl) benzene (PDDPE). It was shown that 2 mol of the living

polymer reacts rapidly with the DPE derivatives to form the dilithium adduct in hydrocarbon

solvents, whereas in THF monoaddition is reported. Moreover, PDDPE exhibited less tendency

to form the corresponding diadduct in both hydrocarbon solution and in the presence of THF.

Taking into account the above observations, a three-arm asymmetric PS star was successfully

prepared (Figure 5-4).362

The monoadduct product was reacted with a second polystyryllithium chain, having

different molecular weight, to form the coupled product. The efficiency of this coupling reaction

depends on the control of the stoichiometry between the reactants. Under optimum conditions the

efficiency of the coupling reaction can be higher than 96%. Finally, the addition of styrene leads

to the formation of three-arm asymmetric PS stars.362 The polymerization took place in the

presence of THF to accelerate the crossover reaction. The SEC analysis showed the existence of a

small quantity of the monoadduct product and the second arm of the PS homopolymer, due to

incomplete linking reactions. The weak points of the method are the great care that should be









exercised over the stoichiometry of the reactions and the inability to isolate and consequently

characterize the third arm. However, the method is valuable, since it provides the possibility to

functionalize the third arm by reaction with a suitable electrophilic agent.

More recently Hirao and colleagueS363-36 developed a general method employing DPE

derivatives carrying protected chloromethyl groups. PS asymmetric stars of the types AA'2,

AA'2A"2, AA'3, AA'4, AA'A"2, and AA'4A"14 were prepared by this method. The whole procedure

is based on the reaction sequence shown in Figure 5-5. Living PS was reacted with 1,1-bis(3-

methoxymethylphenyl) ethylene followed by transformation of the methoxymethyl groups to

chloromethyl groups using BCl3 in CH2 12 at 0 oC for 10-30 min. Despite the difficult multistep

procedure of this method, it was shown that polystyrenes with predictable molecular weights,

narrow molecular weight distributions, and almost nearly quantitative degrees of

functionalization could be synthesized. Small amounts (<5%) of coupled PS byproducts can be

produced during the transformation reaction, due to a Friedel-Crafts side reaction among the

polymer chains. Following the same scheme, AB2 miktoarm stars, where A is PS and B is PI or

PtBuMA, were synthesized by Hirao and Hayashi.364 In the latter cases, a small amount (5%) of

the dimeric product was observed by SEC analysis. It was proposed that this byproduct is

obtained by the Li-Cl exchange and/or electron transfer reactions.

5.1.2 Dendrimer-like Polymers

5.1.2.1 Introduction to dendrimers

The term "dendrimer" coming from the greek words "dendron" (trees) and "meros" (part)

was introduced for the first time by Tomalia to describe the highly branched structure of the

poly(amidoamine)s (PAMAM).366,367 Dendrimers are globular, size monodi sperse

macromolecules centred on a central focal point or plurifunctional core (No functions) from









which branches of different generations emerge radially in the three directions of the space. The

branches (repeat units) are connected between branching points of precise functionality Nb,

symmetrically distributed around the core, with the terminal reactive functions F (number of

terminal functions = Nb X cN)G with G, the number of generations) located at the periphery of the

dendrimer (Figure 5-6a). Because of the high connectivity of their repeating units, which in turn

shape them into globular structures, these highly branched macromolecules exhibit unique

properties and have been extensively investigated for a wide range of applications, including

catalysis,368-372 biological molecular recognition,373-375 where dendrimers can engage in host-

guest interactions, energy and electron transfer,334,376,377 and surface modiaication.378

It is well-documented, however, that a distinction should be made between "regular"

dendrimers332,335,350,370,379-381 and hyperbranched polymers,331,348,349,351,382,383 although both exhibit

similarities not only from a structural viewpoint (Figure 5-6a and b), but also regarding their

overall properties in solution or in bulk. The former species are prepared in stepwise fashion by

repeating a sequence of coupling/modiaication reactions and exhibit a perfectly defined

architecture with a degree of branching equal to unity. In contrast, hyperbranched polymers are

generally synthesized in a non-iterative one-pot polymerization procedure from ABn-type

monomers, where A and B are antagonist functional groups. Therefore these hyperbranched

structures exhibit an irregular architecture (Figure 5-6b) with incompletely reacted branch points

throughout the structure (much higher polydispersity compared to dendrimers and degree of

branching generally ranging from 0.5 to 0.6).

Two complementary general approaches, the divergent and the convergent, have been

used for the synthesis of dendrimers (Figure 5-7).332,384-386

The divergent approach developed by Tomalia366,367 and Newkome387 in 1985 consists in

the growths of branches which starts at the multifunctional core and proceeds radially outward









toward the dendrimer periphery. Successive generations have been prepared in a stepwise fashion

by repeating a sequence of coupling/modification reactions.

The concept of repetitive growth with branching was first reported in 1978 by Voigtle and

colleagues388 who developed an iterative "cascade" method for the synthesis of low molecular

weight branched polyamines by repeating a two-step cycle: the Michael addition of acrylonitrile

on amine functions, and then the reduction of the nitrile functions into amine functions (Figure 5-

8). The low yield of the reduction step due to cyclization side-reactions and the difficulties met

during the purification forced them to stop at the second-generation. Even though, these objects

could not be considered as "true dendrimers", this was the first attempt in synthesizing

dendrimers. A decade and a half later, two research groups, the Miilhaupt389 and Meij er390 (DSM)

ones, significantly improved this approach developed by Voigtle leading to well-defined true

poly(propylene imine) dendrimers. The route developed by the DSM group is particularly worth

mentioning because it constitutes a viable commercial route to this family of aliphatic amine

dendrimers.

However, the first paper published on the macromolecular synthesis of"true dendrimers"

also called starburstt" polymers was reported by the Tomalia's group366 (Dow Chemical Co.).

Using chemistry and conditions less prone to cyclization side-reactions and therefore more

suitable for repetitive growth, Tomalia et al. disclosed the synthesis and characterization of the

first family of dendrimers in 1984-1985.366,367 The synthesis was initiated by Michael addition of

a "core" molecule of ammonia to three molecules of methyl acrylate, followed by exhaustive

amidation of the triester adduct using a large excess of ethylenediamine, a process that generates

a molecule with six terminal amine groups (Figure 5-9). Iterative growth is then continued using

alternating Michael addition and amidation steps with the appropriate excess of reagents.

Optimization of this procedure enabled the synthesis of globular poly(amidoamine) (PAMAM)









dendrimers (up to tenth generation) on a commercial scale with molecular weights well above 25

000.

Shortly thereafter, in 1985, Newkome reported preliminary results toward another family

of trisbranched poly(ether amide) hydrosoluble dendrimers,387 also called "arborols" because of

the terminal hydroxyl functions at the periphery. This divergent approach involves a repetitive

multi-step cycle: a Williamson etheration reaction on the multifunctional core, an introduction of

-C(CO2Et)3 grOups activated by tosylation and an amidation using

tri s(hy droxym ethyl)ami nom ethane (F figure 5 10). The u se of AB 3-typ e group s m ake s the growth s

of the dendrimer faster with a second-generation dendrimer carrying 27 hydroxyl-terminal

functions (33)

Several other novel applications of the divergent approach have recently appeared,

leading to silicon- (siloxane, silane, carbosilane, etc.. .)156,379,391-406, phosphorus-379,407-411, boron-

379,412-417, Or germamium-contalmnng379,418 dendrimers, giant polyallyl dendrimers,372,419,420 and

organometallic dendrimers.372,421 All these different works have shown that given an appropriate

choice of coupling and activation steps, reagents, and reaction conditions, the divergent approach

is ideally suited for the large-scale preparation of dendrimers as the quantity of dendrimer sample

essentially doubles with each generation increment. The rapid increase in the number of reactive

groups at the chain ends of the growing macromolecule is a significant feature of all the divergent

approach es.42

However, this leads to a number of potential problems as growth is pursued. Firstly, any

incomplete reaction of these terminal groups would lead to imperfections or failure sequences in

the next generation; the probability of this occurring increases as the growing macromolecule

increases. Secondly, to prevent side reactions such as cyclizations or coupling of starburstt"

molecules and to force reactions to completion, extremely large excess amounts of reagents are









required in latter stages of growth.423 These large excesses must be completely removed before

continuing with the next-generation growth step in order to prevent the initiation of new growth

centers.42

In 1989-1990, Hawker and Frechet introduced the "convergent" growth approach to

dendrimers,424,425 the second general route to dendritic structures. The convergent growth, first

demonstrated with poly(ether) dendrimers, starts at what will become the periphery of the

molecule proceeding "inward" to afford building blocks (dendrons) that are subsequently coupled

to a branching monomer through reaction of a single reactive group located at its "focal point"

(Figure 5-7). The strategy developed by Frechet and co-workers for the poly(benzyl ether)

synthesis is based on two repetitive steps (Figure 5-11): the Williamson coupling reaction of the

benzylic bromide on the phenolic groups of the 3,5-dihydroxybenzyl alcohol used as the

monomer and then a bromination step of the focal benzylic alcohol function in presence of CBr4

affording brominated dendron. Subsequent repetitions of the Williamson coupling and

bromination steps, and purification after each steps, enabled the production of the sixth

generation dendrons with molecular weight distribution close to 1 and good control over

molecular weights.

This convergent strategy allows both for a drastic reduction in the amount of reagents

used and for intermediate purification at each step of growth. More importantly, the convergent

growth allows unparalleled control over functionality at specified locations of the growing

macromolecule, and it provides access to numerous novel architectures through the attachment

of dendrons to other molecules.425-427 This has led to different dendrimers based on aryl

ether425,427,428, aryl alkene429-434, aryl alkyne435-439, phenylene426,440-442, alkyl ester443-445, alkyl

ether446,447, Or other type332 Of repeating units, and to innovative dendritic architectures such as

dendrimers with chemically varied layers or encapsulated functional entities,448,44 dendrimers









with differentiated "surface" functi onaliti es, 450,451 linear-b-dendron hybrid dendritic

macromolecules consisting of a linear polymer block with either one or two dendrimers chain

ends,22~5~5 metalloporphynin dendnimers,45 or also dendritic fullerenes.45~5

5.1.2.2 Dendrimers with "true" macromolecular generations or dendrimer-like polymers

This is only 10 years that the "dendrimer-like star polymers", term coined by Hedrick,347

have first appeared with the preparation of third generation dendrimer-like poly(ethylene oxide)

(PEO) by Gnanou and Six346 in 1995 in a report where they showed that polymeric chains could

be connected between branching points regularly distributed within a dendritic structure. These

architectures exhibit a similar structure to the well-known "regular" dendrimers (a central core, a

precise number of branching points, and outer terminal functions) but carry true polymeric chains

(in opposition to the regular dendrimers) connected by branching points regularly distributed

within the dendritic structure (in opposition to the hyperbranched polymers) (Figure 5-6c and

d).346,347,460 Therefore, the arborescent architecture of these dendrimer-like polymers give to these

radially, topologically layered and isomolecular branched architecture a better solubility and a

lower viscosity compared to the linear homologues.

More recently the improvement of such a synthesis, relying on the reiteration of two same

steps that are the anionic polymerization of ethylene oxide from multifunctional alkoxides and

the chemical modification of the chain ends in order to introduce the branching points and two

new initiating sites for each branches for the next generation, allowed Gnanou and colleagues to

prepare a dendrimer-like poly(ethylene oxide) up to the eighth generation with a molar mass of

900 000 g.mol-l and 384 external hydroxyl functions (Figure 5-12).461

The same group adopted a similar approach to engineer PSn-b-PEO2n462 and PEOn-b-

PS2n463 dendrimer-like amphiphilic copolymers by combining atom transfer radical

polymerization (ATRP) of styrene and anionic ring-opening polymerization (AROP) of ethylene









oxide. The general approach for introducing branching points at the PEO or PS termini consists

in transforming the end-groups of these polymers into twice as many functions that can

subsequently serve to initiate the polymerization of either the same or another monomer by

ATRP or AROP (Figure 5-13). The switch from ATRP of styrene to AROP of ethylene oxide,

and vice versa were achieved by chemical modification of brominated PS chain ends to generate

twice the number of hydroxyl groups for the anionic polymerization of EO, and by selective

functionalization of oxanionic sites of PEO into twice the number of 2-bromoisobutyrate groups

for the ATRP polymerization of styrene, respectively. 462,463

More recently, Gnanou and co-workers were successful in synthesizing (PSn-b-PS2n-b-

PS4n) dendrimer-like polystyrene of third generation464 and (PSn-b-PAA2n) pOlystyrene-b-

poly(acrylic acid) dendrimer-like copolymers465 based on calixarene cores by using exclusively

ATRP in combination with chain end modifications. Calixarene-based cores were used as

initiators for ATRP of styrene yielding star polymers containing precisely 4, 6, or 8 arms. The

latter were modified in a two-step sequence of two chain end modifications to introduce the

branching points and at the same time multiply by a factor of 2 the number of initiating sites for

the next generation so as to generate PS stars carrying 8, 12, or 16 terminal bromoisobutyrate

groups, respectively (Figure 5-14). These precursors served as multifunctional macroinitiators for

the formation of the second generation of dendrimer-like PS. Reiteration of the aforementioned

sequence of reactions allowed to derive dendrimer-like polystyrene of third generation that were

constituted of 16, 24, or 32 outer arms, respectively. The latter dendrimer-like PS demonstrated

similar viscosity behavior with the "regular" dendrimers.464

Using a variation of this divergent "grafting from" approach, the Hedrick group347,466-468

derived an entire array of dendrimer-like polyesters and related copolymers by successive

grafting of polylactones and polylactides obtained by ring-opening polymerization and









polymethacrylic blocks by ATRP. A hexahydroxyl-functional core 2,2-bis(hydroxymethyl)

propionic acid derivative was used as an initiator for the stannous-2-ethylhexanoate-catalyzed

"living" ring opening polymerization (ROP) of e-caprolactone, L-lactide, and racemic L,D-

lactide producing a hydroxyl terminated six arm star polymer with controlled molecular weight

and narrow polydispersities (PDI < 1.1) (Figure 5-15). Branching junctions at the chain ends

were introduced with benzylidene-protected 2,2-bis(hydroxymethyl) propionic acid. Subsequent

generations were then polymerized, after deprotection, from these star-shaped macroinitiators

(Figure 5-15). Successive chain end capping and initiation produced three generations of

polymers with molecular weights in excess of 130,000 g/mol and narrow polydispersities

(<1.20).468

The capping of the six-arm star chain ends with dendrons containing activated bromide

moieties could also produce "macro-initiators" for atom transfer radical polymerization (ATRP).

Methyl methacrylate was thus polymerized from these "macro-initiators" in the presence of an

organometallic promoter to produce the requisite dendrimer-like star polymers.466

Not fundamentally different either was the synthetic scheme followed by Percec et

al 469,470 for the synthesis of dendrimer-like polymethacrylates of third generation. Starting from a

trifunctional initiator for the copper-catalyzed living radical polymerization of methyl

methacrylate, they developed multipurpose compounds-named TERMINI-acting as chain

terminators as well as reinitiators and served to introduce branching points (Figure 5-16). After

demasking, the TERMINI repeat unit enables the quantitative reinitiation, in the presence or

absence of a catalyst, of the same or a different living polymerization, thus becoming a branching

point (Figure 5-17). The demonstration of this concept was made by using a combination of









metal-catalyzed living radical polymerization (LRP) and as TERMINI, to elaborate dendritic

macromolecules based on methyl methacrylate (MMA).469

In contrast, Hadjichristidis and Chalari471 followed a convergent approach to assemble

their dendrimer-like copolymers of styrene (S) and isoprene (I), the central core being built in this

case in the last instance. Such dendritic copolymers were obtained via anionic polymerization

using a dual-functionality compound as a branching agent and trichloromethyl silane or

tetrachlorosilane as deactivators to build the central core. First, the succession of three different

steps: the selective reaction of a living chain with the chlorosilane group of 4-

(chlorodimethyl silyl)styrene (a dual-functionality compound) to produce a macromonomer, the

addition of a second living chain (same or different) to the double bond of the macromonomer,

and the polymerization of isoprene initiated by the anionic sites, allowed the synthesis of off-

center "living" graft polymer (Figure 5-18). Finally, the reaction of the produced off-center living

species with trichloromethylsilane or tetrachlorosilane leads to the synthesis of second-generation

dendritic macromolecules (S21)3, (SI'I)3, ('1)3, and (I'21)4.

More recently, the same group472 adopted a similar approach to engineer a series of well-

defined second (G-2) and third (G-3) generation dendritic polybutadienes (PB) synthesized by the

coupling of the living G-2 and G-3 dendrons with methyltrichlorosilane, using anionic

polymerization high-vacuum techniques (Figure 5-19). The synthetic approach of the living G-2

and G-3 dendrons involves the repetition of (a) the synthesis of an in-chain double-bond PB by

selective replacement of the two chlorines of 4-(dichloromethyl silyl)-diphenyl ethylene

(DCMSDPE), a linking reagent with dual functionality, with PB by titration with PBLi (or living

G-2 dendrons), (b) the addition of s-BuLi to the double bond, and finally (c) polymerization of

butadiene from the newly created anionic site (Figure 5-19).









Quirk and co-workers473 Synthesized a series of three end-branched, star-branched

polystyrenes with 6, 9, and 13 end branches by the linking reactions between three-arm

polystyrene star precursors end-functionalized with different chlorosilane linking agents and an

excess of poly styrene-b-(oligobutadi enyl)1ithium (P S-b-B ~Li ). By using thi s coupling reacti on

between three-arm trichlorosilane end-functionalized polystyrene stars and an excess of (PS-b-B

Li ) living chains, they were able to obtain a second-generation dendritic architecture (Figure 5-

20).473

Very recently, the Hirao group474,475 also proposed a convergent approach involving

coupling reactions of living anionic poly(methyl methacrylate)s (PMMA) and functionalization

of chain ends to derive dendrimer-like polymethacrylate-based systems up to seventh generation.

This two-step sequence of reaction involves a coupling reaction of R-functionalized living

PMMA with two tert-butyldimethyl silyloxymethylphenyl (SMP) groups with benzyl bromide

(BnBr) chain-end-functionalized PMMA and a transformation reaction of the introduced SMP

groups into BnBr functionalities. The dendrimer-like star-branched PMMAs up to the seventh

generation have been successfully synthesized by repeating these two reactions seven times

(Figure 5-21).475

5.2 Results and Discussion

5.2.1 Synthesis of Asymmetric and Miktoarm Star Polymers

We previously described the synthesis of a new category of tri- and tetracarbanionic

initiators by the halogen-lithium exchange reaction between a tri- or tetrabromocompound and

sec-butyllithium (Chapter 3).121 These multicarbanionic initiators were first used for the anionic

polymerization of styrene and butadiene to result in well-defined tri- and tetraarmed polystyrene

and polybutadiene stars exhibiting monomodal and narrow molar mass distribution.121 These









pluricarbanionic initiators were also employed to obtain (PB-b-PEO)n amphiphilic diblock219 and

P(S-b-B-b-MMA)n (n = 3 or 4) triblock star copolymers.121 The same halogen-lithium exchange

reaction was applied here, but in this case a ,o'-dibromo end-functionalized chain polymer was

used instead of small multibromo molecules.

5.2.1.1 Introduction of the branching point at the chain end of a linear polymer

The first objective of this work was the introduction of a dibromo end group, whose

halogen atoms are carried by separate aryl rings. We tried in a first attempt the reaction of

polystyryllithium living chains with 4,4'-dibromodiphenylethylene. Unfortunately, as

demonstrated by size exclusion chromatography (SEC) analysis after methanol quenching

(Figure 5-22), three different populations could be observed corresponding for the first peak (1)

in the low molar mass region to the PS chain functionalized by the dibromo compound and for

the two other peaks (2 and 3) in the high molar mass region to the PS after the coupling reaction

on either one or two bromide positions (Figure 5-22). That demonstrated that the

polystyryllithium living chain end is too nucleophilic to react only on the insaturation and thus to

obtain pure mo,c'-dibromo end-functionalized chain polymer.

The reactivity of the living chain ends of the polystyrene chains was thus reduced by

replacing the alkyllithium chain ends by less reactive potassium alkoxide living chain ends. For

this purpose, we used hydroxyl-terminated commercial linear PEO and hydroxyl-terminated

linear PS or PB synthesized using sec-butyllithium as initiator in cyclohexane and an excess of

ethylene oxide to deactivate the living chain ends. The latter were well-characterized by 1H NMR

spectroscopy demonstrating a quantitative functionalization. The hydroxyl functions of these

linear polymer chains were first deprotonated in the presence of a stoichiometric amount of

diphenylmethylpotassium (DPMK) in THF to give potassium alkoxide living chain ends and then









a solution of an excess of 4,4'-dibromodiphenylethylene (4 equivalents per hydroxyl group) in

THF was added to the mixture (Figure 5-23). The SEC analysis of the polymer after methanol

quenching demonstrated this time the presence of only one peak with a small shift to the high

molar mass region after the functionalization by the dibromo compound (Figure 5-24).

Indeed, the 1H NMR spectra of the PEO-(PhBr)2, PS-(PhBr)2 and PB-(PhBr)2 Samples of

low molecular weight showed the total disappearance of the signal at 6 = 5.4 ppm corresponding

to the unsaturation of the dibromo compound and exhibit signals at 6 = 6.9-8.0 ppm assignable to

the aromatic protons -CH2--CH(PhBr)2 at the chain end and at 6 = 4.2 ppm (in the case of PEO)

or 6 = 3.7 ppm (in the case of PS or PB) corresponding to the protons carried by the primary

terminal carbon groups -CH2-CH(PhBr)2 (Figures 5-25 and 5-26). Specifically, the

experimental functionality values calculated by the ratios of resonance signals at 6 = 3.3 or 0.9

ppm (methyl protons of the initiator -CH3 in the cases of PEO or PS and PB, respectively) with

those at 6 = 6.9-8.0 ppm assignable to the aromatic protons at the chain end are always close to 1.

The same experimental functionality close to 1 was obtained by the ratios of resonance signals at

6 = 3.6 ppm ((OC2CH2)n methylene protons of the PEO chains) or at 6 = 4.9-5.8 ppm (protons

of the double bonds of the PB chains) with those at 6 = 6.9-8.0 ppm assignable to the aromatic

protons at the chain end.

As well-known, following the reactivity scale of the nucleophilic conjugated base, it

should be impossible for an alkoxide group, which is not nucleophilic enough, to react with an

unsaturation. However, these results demonstrate that in the case of the 4,4'-

dibromodiphenylethylene the potassium alkoxide living chain end is able to react with the

unsaturation. Futhermore, the reaction of living end-functionalized PEO with diphenylethylene

was tried. In this case, no addition on the diphenylethylene unsaturation was observed by 1H









NMR spectroscopy. This demonstrates the influence of the halogen atoms carried by the aryl

rings, which have an electron withdrawing and thus an activation unsaturation. Therefore, the

unsaturation is reactive enough to react with a potassium alkoxide living chain end. All these

proofs attest to the synthesis of pure well-defined m,o'-dibromo end-functionalized PEO, PS and

PB chains, which can be now used for the synthesis of polylithium macroinitiators by the

halogen-lithium exchange reaction.

5.2.1.2 Preparation of pluricarbanionic macroinitiators for star polymer synthesis

These different m,o'-dibromo end-functionalized PS and PB chains were treated with

stoichiometric amounts of sec-butyllithium in benzene or cyclohexane to generate the

corresponding dilithiated species in presence of 2-bromobutane (Figure 5-23). These polylithiated

species were found to be totally soluble in apolar solvents such as cyclohexane or benzene. To

neutralize the 2-bromobutane, which could deactivate the living polymer chains, and prior to

monomer addition some equivalents of sec-butyllithium were added giving the formation of 3,4-

dimethylhexane (Figure 5-23). The polymerization of different monomer such as styrene,

butadiene or isoprene were performed using different polylithiated macroinitiators such as PS-

(Ph-i )2, Or PB-(Ph-Li )2 in CyClOhexane or benzene at room temperature without any additives.

These different asymmetric or miktoarm star samples were analyzed by SEC, size exclusion

chromatography with a light scattering detector (SEC/LS), and 1H NMR spectroscopy. Table 5-1

gives the data pertaining to these asymmetric and miktoarm star (co)polymers obtained from

polylithium macroinitiators. Samples of narrow molar mass distribution (1.01< 2v/2, <1.15)

were obtained. The complete disappearance of the peak of the PS-(PhBr)2 and PB-(PhBr)2

precursors on the chromatograms meant that all precursor chains participated in the

polymerization (Figures 5-27, 5-28 and 5-29).









The absolute molecular weight values drawn from SEC/LS were found to be higher than

those obtained by SEC, especially in the case of asymmetric three-arm PS stars, and agreed well

with the theoretical molecular weight, attesting that two polymer arms of well-controlled size

could be grown from each linear chains and thus a compact architecture is obtained (Table 5-1).

The structures of the polymers formed and especially the star character could also be

established by 1H NMR analysis on asymmetric and miktoarm star samples with low degrees of

polymerization (Figure 5-30 and Table 5-1). From the ratio of the integration values of the signal

of the methyl protons -CH3 Of the initiator at 6 = 0.9 ppm to that of the methylene protons of the -

CH20H chain ends (6 = 3.6 ppm), the actual functionality of various samples prepared could be

determined: functionalities close to 2 for the two arms grown from the branching point of the

asymmetric and miktoarm star (co)polymers (Figure 5-30 and Table 5-1). Indeed, the hydroxyl

end groups of the different samples of asymmetric and miktoarm star polymers were titrated in

THF by a solution of DPMK of known concentration ([DPMK] = 0.521 mol.L^)~. The results of

these titrations demonstrated functionalities close to 2 for all the stars (Table 5-1).

5.2.2 Synthesis of Dendrimer-Like Polystyrene and Polybutadiene

The same procedure as in the case of the preparation of the asymmetric and miktoarm star

polymers was followed here for the synthesis of dendrimer-like polymers, but in this case a

multifunctional initiator was used instead of a monofunctional one.

5.2.2.1 Synthesis of star-shaped (G-1) polystyrene and polybutadiene precursors

The first step of the procedure is the synthesis of the tetracarbanionic initiator based on

the halogen-lithium exchange reaction. As previously described (Chapter 3), a

tetrabromocompound is treated with stoichiometric amounts of sec-butyllithium in benzene to

generate the corresponding tetraalkyllithium agent (Figure 5-31).121 The resulting polylithiated









species being insoluble in benzene, tetramethylethylene diamine (TMEDA) (ratio of

[TMEDA]/[Li] = 2) was utilized to solubilize the polyalkyllithium species due to the complex

formed between the lithiated species and the ligand. These complexes give stable species and

enough steric bulk to prevent aggregation of the polylithiated initiators. As shown previously,

minor amounts of the side product 2-bromobutane, which could deactivate "living" carbanionic

sites, were neutralized by a small excess of sec-butyllithium yielding 3,4-dimethylhexane as an

inert byproduct. The anionic polymerization of styrene and butadiene were carried out in benzene

at room temperature using the solubilized tetralithiated initiator at a concentration of 5.3 x 10-2

M. After complete conversion of the monomer, end capping was accomplished by adding a large

excess of ethylene oxide.

The characteristics of these star samples are listed in Tables 5-2 and 5-3. The

characterization of all the samples by size exclusion chromatography (SEC) showed the

disappearance of the peak at low molecular weight region, implying total consumption of the

tetrafunctional initiator by styrene and butadiene polymerization (Figure 5-32). The actual

molecular weight of the hydroxyl chain end polystyrene and polybutadiene stars determined by

SEC/LS were found to be in good agreement with the calculated values and their distributions

were narrow (2y/2, < 1.1). The tetrafunctionality of the resulting polystyrene and polybutadiene

stars were then demonstrated by 1H NMR spectroscopy analysis of star samples with low degrees

of polymerization for each arm (Figure 5-33).

Specifically, the experimental functionality values calculated by the ratios of resonance

signals at 6 = 6.8-8.0 ppm (aromatic protons of the tetrafunctional initiators) with those at 6 = 3.6

ppm (-CH2-OH chain end protons) are always close to 4 for the four-armed stars. Further









evidence for the four-arm star structure was obtained by comparing the intrinsic viscosity [r] of

our samples with that of linear polymers, as previously demonstrated.121

5.2.2.2 Introduction of the branching points at each arm end

The next step in the synthesis of these dendrimer-like polymers was the introduction of a

branching point and thus two geminal aryl bromide groups at each chain end of the stars. The

same procedure as in the case of the preparation of asymmetric and miktoarm star polymers was

followed. The hydroxyl functions at the chain ends of the polystyrene and polybutadiene stars

were deprotonated in presence of a stoichiometric amount of DPMK in THF and then a solution

of 4,4'-dibromodiphenylethylene in THF was added. After the deactivation of the living chain

ends by methanol addition, the resulting functionalized star polymers were analyzed by SEC and

1H NMR spectroscopy (Figures 5-32 and 5-34). First, it can be observed by SEC, as in the case of

linear chain polymers, a small shift of the peak to the high molar mass region and the absence of

secondary peaks in the high molar mass region attesting that no coupling reactions occurred on

the bromide positions. The good functionalization of the chain ends of each arm of the

PB4(PhBr)s star polymers was established by 1H NMR analysis on polybutadiene samples with

low degrees of polymerization (Figure 5-34). Indeed, the 1H NMR spectrum exhibit signals at 8 =

6.9-8.0 ppm assignable to the aromatic protons -CH2--CH(PhBr)2 at the chain end and 6 = 3.7

ppm and 6 = 3.5 ppm corresponding to the protons carried by the primary terminal carbon groups

-CH2--CH(PhBr)2 and -CH2-O-CH2-CH(PhBr)2, TOSpectively (Figure 5-34). The

experimental functionality was determined by the comparison of the integration values of the

signals of the aromatic protons of the polyphenylene core and the dibromo end groups (6 = 6.5-

8.0 ppm; 54H) with that of the signals of the protons carried by the primary terminal carbon

groups -CH2--CH(PhBr)2 (6 = 3.7 ppm; 8H) and -CH2-O-CH2-CH(PhBr)2 (6 = 3.5 ppm; 8H).









The ratio of 6.7 found between the intensities of the signals appearing at 6 = 6.5-8.0 ppm and the

one at 6 = 3.7 ppm indicated that functionalization occurred quantitatively (Figure 5-34).

5.2.2.3 Preparation of pluricarbanionic initiators for second generation (G-2) dendrimer-
like polystyrene and polybutadiene synthesis

PS4(PhBr)s and PB4(PhBr)s ,o'-dibromo end-functionalized polystyrene and

polybutadiene stars were treated with stoichiometric amounts of sec-butyllithium in benzene to

generate the corresponding polylithiated species PS4(Ph-Li )s and PB4(Ph-Li )s in presence of 3,4-

dimethylhexane after neutralization of 2-bromobutane. The addition of TMEDA (ratio of

[TMEDA]/[Li] = 2) was necessary to solubilize the latter polylithiated species in benzene. The

polymerizations of styrene and butadiene were performed in benzene at room temperature using

the polylithiated species PS4(Ph-Li )s and PB4(Ph-Li )s, respectively (Figure 5-31). After

deactivation of the living chain ends by addition of an excess of ethylene oxide, the dendrimer-

like polystyrene and polybutadiene obtained were analyzed by SEC and 1H NMR spectroscopy

(Figures 5-35, 5-36, and 5-37). First, the complete disappearance of the peaks of the PS4(PhBr)s

and PB4(PhBr)s precursors on the chromatograms of the PS4PSs(OH)s and PB4PBs(OH)s (Figures

5-35 and 5-36), respectively, showed that all precursor chains participated in the polymerization.

Unfortunately, two other small populations were observed in the high molar mass region either in

the case of hydroxyl-terminated dendrimer-like PS or PB which could be due to the strong

aggregation of the end groups in THF (Figure 5-3 5).

To break this strong aggregation of the terminal end groups at the periphery of the

dendrimer-like polymers, the different samples were characterized by high temperature size

exclusion chromatography (SEC/HT) in dichlorobenzene at 130 OC equipped with a viscometer

detector giving the absolute molar mass. In this case, no population corresponding to these

aggregates and only one peak with a monomodal and narrow molar mass distribution (1.01<









2Mw/2M <1.2) were observed (Figures 5-36 and Tables 5-2 and 5-3). Indeed, the molar mass

values determined from SEC/HT agreed well with the calculated values attesting that two PS or

PB arms of well-controlled size could be grown from each of these branching points.

As to the characterization by 1H NMR spectroscopy of the second generation

PB4PBs(OH)s dendrimer-like polybutadiene (Figure 5-3 7), it clearly revealed the presence of four

signals: the signals of the aromatic protons of the polyphenylene core (22H) and the branching

points at 6 = 6.5-8.0 ppm (32H at the branching points), the signals of the methylene protons

carried by the branching points and at the chain ends -CH2-CH--(PhCH2)2-- at 6 = 3.7 ppm

(8H), -CH2-O-CH2-CH-(PhCH2)2- and -CH2-OH at 6 = 3.4 ppm (24H), and -CH2--

CH-(PhCH2)2- at 6 = 2.8 ppm (4H). The ratios of 6.8, 2.2 and 13.8 found between the

intensities of the signal appearing at 6 = 6.5-8.0 ppm (54H) and the ones at 6 = 3.7 ppm (8H), at

6 = 3.4 ppm (24H) and at 6 = 2.8 ppm (4H), respectively, indicated that initiation occurred with

perfect efficiency (Figure 5-37). Indeed, the titration of the hydroxyl end groups at the periphery

of the PS and PB dendrimer-like polymers in THF by a solution of DPMK of known

concentration ([DPMK] = 0.521 mol.L 1) demonstrated either in the case of PS or PB dendrimer-

like polymers functionalities close to 8 (Tables 5-2 and 5-3). The good definition of these

PS4PSs(OH)s and PB4PBs(OH)s second generation dendrimer-like polymers prompted us to

prepare dendritic polymers of higher generation.

5.2.2.4 Third-generation (G-3) dendrimer-like polystyrene and polybutadiene

This methodology based on the iterative divergent approach as described above was

repeated here (i. e., chain end modification and polymerization of styrene or butadiene) for the

synthesis of dendritic polymers of higher generation. Similar to the cases of G-1 and G-2, the

hydroxyl end groups at the periphery of the PS4PSs(OH)s and PB4PBs(OH)s dendrimer-like









polymers were deprotonated by reaction with stoichiometric amounts of DP1VK and a solution of

an excess of 4,4' -dibromodiphenylethylene was added (4 equivalents per -OH group). After

deactivation of the living chain ends by addition of methanol, the resulting PS4PSs(PhBr)16 and

PB4PBs(PhBr)16 dendrimer-like polymers were characterized by SEC, SEC/HT and 1H N1VR

spectroscopy. As previously shown, no secondary coupling reactions on the bromide positions

were observed. Indeed, the 1H N1VR analysis of the chain ends of the PB4PBs(PhBr)16 dendrimer-

like polybutadiene clearly indicates four distinct signals corresponding respectively to the

aromatic protons of the polyphenylene core, of the aryl rings of the branching points and of the

chain ends (6 = 6.8-8.0 ppm; 118H), and to the methylene protons carried by the branching points

and the chain ends -CH2--CH--(PhCH2)2-- at 6 = 3.7 ppm (24H), -CH2-O-CH2--CH--

(PhCH2)2- at 6 = 3.4 ppm (24H), and -CH2--CH--(PhCH2)2-- at 6 = 2.8 ppm (12H) (Figure 5-

38). In addition, the experimental -PhBr functionality, determined from the ratios of the

integration values of the different signals at 6 = 6.8-8.0 ppm, 6 = 3.7 ppm, 6 = 3.4 ppm, and 6 =

2.8 ppm were found to correspond to the expected value of 16 groups per dendrimer-like

polymer.

Next, the resulting PS4PSs(PhBr)16 and PB4PBs(PhBr)16 dendrimer-like polymers were

treated with stoichiometric amounts of sec-butyllithium in benzene to generate the corresponding

polylithiated species PS4PSs(Ph-i )16 and PB4 PBs(Ph-i )16. At this stage of 16 carbanionic sites

per polymer, a physical gel was formed due to the stronger aggregation of the polylithiated

species in benzene. After the addition of some equivalents of TMEDA (2 equivalents per -PhLi),

the polylithiated species were totally soluble in benzene and the monomer was polymerized. The

living chain ends were deactivated by addition of an excess of ethylene oxide and the resulting

dendritic polystyrene and polybutadiene were characterized by SEC, SEC/HT and 1H N1VR









spectroscopy. As shown in Figures 5-36, the SEC/HT profiles of the PS4PS8PS16(OH)16 and

PB4PB8PBl6(OH)16 third-generation dendrimer-like polymers exhibit only one sharp monomodal

and narrow peak (1.05
polybutadiene, respectively, with in each case the total disappearance of the second generation

macroinitiator. As in the case of the second generation sample, the hydroxyl end groups at the

periphery of the PS4PS8PS16(OH)16 and PB4PB8PBl6(OH)16 dendrimer-like polymers were

titrated in THF by a solution of DP1VK of known concentration ([DP1VK] = 0.521 mol.L^1) and

demonstrated either in the case of PS or PB dendrimer-like polymers functionalities close to 16

indicating that initiation occurred as expected (Tables 5-2 and 5-3).

5.2.2.5 From the fourth- (G-4) to the seventh-generation (G-7) dendrimer-like polystyrene
synthesis

The same iterative divergent approach as in the case of the synthesis of the third

generation dendrimer-like polymers was applied here for the preparation of fourth- (G-4), fifth-

(G-5), sixth- (G-6), and seventh-generation (G-7) dendrimer-like polystyrenes. Successively, the

hydroxyl end groups at the periphery of different generation (G-4, G-5 and G-6) dendrimer-like

polystyrenes were deprotonated by a solution of DP1VK, functionalized after reaction with 4,4'-

dibromodiphenylethylene, and finally these m,o'-dibromo end-functionalized dendrimer-like

polystyrenes were used after reaction with s-BuLi as pluricarbanionic macroinitiators for the

polymerization of styrene in presence of TIVEDA as additive. After deactivation of the living

polystyryllithium chain ends by an excess of ethylene oxide and degassed methanol,

successively, all the dendritic polystyrene samples of different generation (G-4, G-5, G-6 and G-

7) were characterized by SEC and SEC/HT (Figures 5-35 and 5-36). As in the previous cases, the

same peaks corresponding to the aggregates were observed in the high molar mass region by

SEC. However, the latter were not observed at high temperature as shown in the SEC/HT









chromatograms for the fourth- (G-4), fifth- (G-5), sixth- (G-6), and seventh-generation (G-7)

dendrimer-like polystyrenes (Figure 5-36). As can be seen in Figure 5-36, the SEC/HT peak of

each generation of PS is monomodal and narrow and moves to the high molar mass region with

the total disappearance of the precursor as the iteration proceeds. Indeed, the experimental degree

of -OH functionality was determined by titration of hydroxyl end groups by reaction with a

solution of DP1VK of known concentration ([DP1VK] = 0.521 mol.L^)~. As may be seen in Tables

5-2 and 5-3, the results demonstrate experimental functionalities which are very close to the

expected values. From the fourth-generation, this last method of titration of hydroxyl end groups

has been found to be more efficient than 1H N1VR spectroscopy, because of the intensity of the

resonance signals of the end groups which is too weak compared to the signal of the aromatic

protons of the styrene repeat units. Thus, by the reiteration of the two reaction sequence (i.e.,

styrene polymerization and branching reaction) of this divergent approach a seventh-generation

dendrimer-like PS (G-7) was synthesized with an absolute molar mass Mn~' of 1,920x103 g.mOl-1

and consisted of 256 OH end groups and 508 PS segments.

5.2.2.6 Viscosity behavior of dendrimer-like polystyrenes

In the literature, several papers deal with the viscometric behavior of star polymers,

hyperbranched polymers,35 dendrigrafts,313,338,341,476,477 and regular dendrimers.390,422,478 However

Gnanou and colleagueS464 were the first to demonstrate in the case of third-generation dendrimer-

like polystyrenes synthesized by atom transfer radical polymerization, that dendrimer-like

polymers show a behavior in solution similar to the regular dendrimers. In opposition to the

hyperbranched polymers, whose intrinsic viscosity remains independent of the molar mass, the

trace of log[r] with the generation or the molecular weight of the dendrimer-like PS showed an

evolution where [r] first increases as a function of molecular weight/generation, passes through a









maximum to eventually decrease (bell-shaped curve) as in the case of regular

dendrimers.351,390,422,478 In fact, it is well-known that molecular weight in regular dendrimers

increase exponentially with g according to 2g~ and their hydrodynamic volume grows with g3

[r] varying proportionally to g3/2 ~, it passes therefore through a maximum with increasing g.

For a better comparison with the results that was previously obtained by Gnanou and co-

workers,464 the intrinsic viscosities of our dendrimer-like PS were determined at 35 OC using

toluene as a solvent. First, from the experimental [ rldendritic (meaSured at 35 OC in toluene) and the

[rlinear values (calculated from equation (1) for linear PS of same molecular weight under the

same conditions), the g' ratio [rldendritic [Tlinear (liSted in Table 5-2) was determined. The intrinsic

viscosity was found to be lower than the one corresponding to linear PS (until 30 times lower

than the one of linear PS) and the g' parameter decreased with the generation attesting that the

dendritic structure became more and more compact with increasing the number of generation and

branched segments.

[r] = 1.23 x 10-2 Mno.71 (1)


As shown by the relation between [rl]-which is also inversely proportional to the

hydrodynamic density--and the hydrodynamic volume (VH)

[r] = 2.5NaVH/M~= (10xn/3)NaRH3/M~ (2)

where RH is the hydrodynamic radius and Na the Avogadro number, such a constant [r] in

the particular case of arborescent polymers merely reflects the fact that both VH Of the sample and

its mass (M)1 vary approximately in the same proportion upon increasing the number of

generations. To determine how vary hydrodynamic volumes as a function of g, we resorted to

expression (3) given below, using [ r] and M determined experimentally.









RH = [3M~ r]/10xNa] 1 3 (3)

As shown in Figure 5-39, RH inCreaSes nearly linearly with g for the polystyrene

dendrimer-like polymers with g < 5, indicating that VH thus grows in g3 like regular dendrimers.

However, RH becomes constant from the sixth generation. Above this critical generation (g > 6),

the dendrimer-like structures seem to be too compact to distinguish the RH ValUeS obtained for the

sixth and seventh-generation dendrimer-like polystyrenes.

From the trace of log [rldendritic With the number of generation, we could see that [r]

reaches a maximum corresponding to the third-generation dendrimer-like PS and start to decrease

gradually until the seventh generation (Figure 5-40). The evolution of log [rldendritic aS a function

of log Mn was also plotted (Figure 5-41). The same trend as the one observed for log [ rldendritic VS

number of generation plot is seen here, indicating that [r] is not independent of the molar mass

for dendrimer-like PS in opposition to the hyperbranched polymers.

5.3 Conclusion

This methodology based on chain end modification, and involving the original reaction of

a potassium alkoxide living chain end on the insaturation of 4,4'-dibromodiphenylethylene

affords ,o'-dibromo chain polymers whose halogen atoms are carried by separate aryl rings.

Using halogen-lithium exchange reaction the corresponding polylithiated species could be

prepared, providing an efficient synthetic route to the asymmetric and "miktoarm" star

(co)polymers based on the combination of different polymers such as polystyrene, polybutadiene,

and polyisoprene. By the reiteration of this sequence of reactions, dendrimer-like PS and PB up

to the seventh and third generations, respectively, could be successfully synthesized. The

preparation of dendrimer-like PS of higher generation led us to confirm that this family of










macromolecular architecture has a viscosity behavior similar to that of the regular dendrimers

with [r] passing therefore through a maximum with increasing the number of generation.

This halogen-lithium exchange reaction previously applied by us on multifunctional

halogenated polyphenylene molecules for the synthesis of pluricarbanionic initiators,

demonstrated here his efficiency and utility for the preparation of polylithiated macroinitiators.

This latter observation lets us hope that the same halogen-lithium exchange reaction can be

carried out on linear chain polymers carrying pendant aryl bromide groups for the synthesis of

more complex macromolecular architecture such as brush-type (co)polymers.


Molecular weight
asymmetry


Topological asymmetry


Chemical asymmetry
n"miktoarm" stars)


Functional group asymmetry


Figure 5-1. Representative structures of asymmetric and "miktoarm" star polymers.












PSA Li + (CH3)SiCl3 (excess) a PSA-Si(CH3 21 + LiCl + (CH3)SiCl3


+ PSB Li (excess) ] PSA-Si(CH3)(PSB)2


PSA-Si(CH3 2 ,


Figure 5-2. Synthesis of three-arm asymmetric PS star using chlorosilane as linking agent.




PS Li + (CH3)SiCl2H (excess) 2 PS Si PS


(I)


P2VP LiO + B/r


2 P2VP~


Pt
(I) + (II) 1 (PS)2(P2VP)


Figure 5-3.


Synthesis of (PS)2-b-P2VP miktoarm star copolymer by combination of linking and
hydrosilylation reactions.


PSAH2C. ~H


12. e eH


PAH2C. ~ /C2
PSBL i 2.SC 3 e


PAH2C Pc ,C2P


Figure 5-4. Synthesis of asymmetric PS star using DDPE derivative as coupling agent.


PSALi +













'OCH3


CHOH


3 CH


.OCH3


BCl3


Figure 5-5. Use of DPE derivative as branching agent.


































192











































O central eore
Branching point

STerminal group
-Monomer unit

SPolymeric chain


(c) (d)


Figure 5-6.


Representation of different tree-like macromolecular structures: (a) "regular"
dendrimers; (b) hyperbranched polymer; (c) dendrigraft or arborescent polymer; and
(d) dendrimer-like (star) polymer.















J


J


ctt-
J


Figure 5-7. Representation of dendrimer growth by the divergent and convergent methods.


Second generation


First generation


N Co(II
M

N N

NC CN NC N


NC N N


Co(III)/NaBH4 I
MeOH

NHP NH,


AcOH


BH4




HpN NH2 H7N N


I)/Nal
[eOH


Figure 5-8. Synthetic route developed by Voigtle for the synthesis of branched polyamides.


"a














































Second Generation





Figure 5-9. Synthetic route for the preparation of PAMAM dendrimers by the divergent method.


NH2

O NH


1) 3 O q


2) H2 NN


H
N
H/ \H


HNH2


1) 6 O q0
O

2) H2 NH2,


First Generation


ONH2




ON NH,



O NH2


Generations 3 to 10





















OTs


O- OTs


1) CICH2CO2H,
tBuOK


OHOHH


2) M eL H HH4


4) TsC1, pyridine


NaC(CO2Et)3


E02C CO2Et
OH CO02Et


OCO2tC2Et
K2CO3 O EtO2C CO2Et

Et2CO2Et


Figure 5-10. Synthesis of poly(ether amide) dendrimers.



















1-



~hBr


HO OH K2CO3 18-C-6
HO


HO OH
HO

K2CO3, 18-C-6


1) CBr4, PPh3


K2CO3, 18-C-6


Figure 5-11. Synthesis of poly(benzyl ether) dendrimers by the convergent method.













































gtrifimctional precursor
--- PEO chains

O branching points


i) DPMK
DMSO

O


ii) NaOH/H20;
TBAB/THF;
ally chloride
50 oC

iii) NMO;OsO4


OH


i), ii) and iii)


i>


i), ii) and iii)


Figure 5-12. Synthetic strategy toward dendrimer-like PEO.


OH



HO OH
























~n~vuL~w: PS chains
: PEO chains


HO~NO

D IVI


,CH2Br Styrene, 100 oC
CuBr/2,2'-bipyridyle


DP1VK



THF


Figure 5-13. Synthesis of dendrimer-like copolymers PS3-b-PEO6.












Styrene, 100 oC

CuBr/2,2'-bipyridyle


goctafunctional precursor
aIV PS chains

O branching points

R: -O-C(=0)CH2C(CH3 2Br


1) HO N OH, DMF, 30 OC, 72 h


2) Br XBr, Et3N, THF, RT, 24 h


Styrene, 100 oC

CuBr/2,2'-bipyridyle


Second-generation PSPS16Brl6


Figure 5-14. Synthesis of a second-generation dendrimer-like PS by ATRP.














O


Sn( ct)2


HOUO
H~O O OH



OHOH


"-t~O3~


i) O OOH

ii) H2 / Pd


iii)` Sn(Oct)2
O>


Figure 5-15. Synthesis of a third-generation dendrimer-like poly(L-lactide).














































Cu20 / Bipy
R: TBDMS


I 0C



S 2I









SCONEt2


RO



SCONEt2


MMA

Cu20 / Bipy


Et2NOCS


;CONEt2


~SCONEt2


,NEt2


Figure 5-16. Functionalization of PMMA star chain ends by a TERMINI compound.










CIO2S


CIO2S /OS2

-2S o


Cl2 / HCOOH

Et2NCOCl
SO2






CI OO
-0





02S OCIO2S SO2



s O\
02S02S



ClO 02 / f \/SO

SO2

1-

MMAi






OO








Figure 5-17. Divergent iterative synthetic strategy elaborated for synthesis of dendritic PMMA by
a combination of LRP and TERMINI.






PlorPS


P~PIP orP





M~acromonmar


-L~~


1~


PlorPS

PIorPS

3


SiC13CH3


j~-


-i~"z;


Figure 5-18. Synthesis of a second-generation dendritic P(S2 3) COpolymer.






In chain double bond PB


2.1Buta ine L, CSPEH

Living PB (G 2) dendron ~r


In-chain double bond PB dendron


S~cciC3a


1. s-Bu~i
2. Butadiene


3 LiCl


Living PB (G-3) dendron


G-3 dendritic polybutadiene

Figure 5-19. General reaction scheme for the synthesis of third-generation dendritic PB.











/


C6H5


C6H5


-CH2Bu


+CH2BU
PSLi


CH3SiCl3


CH2Bu BuH2C
Cl2(H3C)SiSP, \PSSi(CH3)C 12

C6H5 C6H5


C6H5 CH2BU
PSSi(CH3)C12


PS-b-oligoB-Li


Figure 5-20. Synthesis of second-generation dendrimer-like PS by coupling reaction of living
chains on chlorosilane star chain ends.












































30 31 32 33 34 36 36 37 38 39 40 41 42 43 44 46
Elution time (min)


~ ...S--
sBS1 r-su """O L1Q
2) (CH,),SIC1/ L~BrBr
3) L~Br


k~---


oi,


Figure 5-21. Synthesis of second-generation dendrimer-like star-branched PMMA.


Br


111E r


Figure 5-22.


SEC trace (RI detector) of polystyryllithium living chains after reaction with 4,4'-
dibromodiphenyl ethylene. Conditions: [4,4' -dibromodiphenyl ethylene]/[P S-i ] 4,
at R.T. in cyclohexane.












cHOOK


- --vvvvnCH2- CH2--OH > ^^^^^^^^^^^ CH2-CH2-O O SK
THF, R.T.


Br



~ vvvvv CH2--CH2--O-CH2--CH



Br


1) H2C-C ,THF, R.T., 10m

Br


2) CH30H


OL i



> Nvvv CH2--CH2--O-CH2--CH


+ 2


1) Monomer
2) CH30H/
^^^^^^r'CH2- CH2- O- CH2 -C H
Benzene, R.T.





~U: PS, PB or PI

cT~\: PEO, PS, PB or PI





Figure 5-23. Synthesis of asymmetric and "miktoarm" star (co)polymers.











PS-OH
Mn,= 2348 g/mol
MMn = 1.04


PS -(B r)2
Mn,= 2809 g/mol
M)Mn 1.06


3~5 36 37 38 3~9 40 41 42 43 44 45 46 47 48

Elut~ion time (min)

Figure 5-24. SEC traces (RI detector) of PS(Br)2 aryl bromide-terminated polystyrene (Run 2,
Table 5-1) and its precursor PS-OH hydroxyl-terminated polystyrene (Run 1, Table
5-1). Conditions: [4,4' -dibromodiphenylethylene]/[PSO-K ] = 4, at R.T. in THF.

















b
HZ

H3C O rl I C )


3.5


CH,CI,


75 7.065 6.0 5.55.0 4.5 4.0


3.0 2.5 240 1.5 140 0.5


Br







Br


CCH, C


611 5.5 51


2.0 15 1.0 0.5


a (pp m)


Figure 5-25. 1H NMR spectra (CD2C 2; 400 MHz) of PEO(Br)2 aryl bromide-terminated
poly(ethylene oxide) (Run 4, Table 5-1) and its precursor PEO-OH hydroxyl-
terminated poly(ethylene oxide) (Run 3, Table 5-1).


4.5 4.0 3.5 3.0 2.5


7.5 7a 6.5







































7.5 7J 65 6.0 55


1.0 0.5


Br


d


h




g


B

h


11


75 7.0 65 6.0 55 5.0 4.5 4.0 3.5 3.0 2.5 2D 1.5 19 0.5
8 (ppm)


Figure 5-26. 1H NMR spectra (CD2 12; 400 MHz) of PB(Br)2 aryl bromide-terminated
polybutadiene (Run 6, Table 5-) and its precursor PB-OH hydroxyl-terminated
polybutadiene (Run 5, Table 5-1).


























26 28 30 32 34 36 38 40 42 44 46 48
Elution time (min)


Figure 5-27.


SEC traces (RI detector) of asymmetric star polystyrenes PS-b-PS2 (Runs 7 (A), 8
(B) and 9 (C3), Table 5-1) and its precursor PS-(Br)2 (Run 2, Table 5-1). Conditions:
[Li ] = 5x10- mOl.L^1, at R.T. in benzene.


26 28 30 32 34 36 38 40 42 44 46 48
Elution time (min)

Figure 5-28. SEC traces (RI detector) of asymmetric star polymer PB-b-PB2 (Run 10 (B), Table
5-1) and "miktoarm" star copolymer PB-b-PS2 (Run 13 (C), Table 5-1) and its
precursor PB-(Br)2 (Run 6 (A), Table 5-1). Conditions: [Li ] = 5x10-3 mOl.L^1, at
R.T. in benzene.


























1; I~ Ib I; "31 3; 1 Ib "4 I 4 1 I~
Elution time (min)



Figure 5-29. SEC traces (RI detector) of "miktoarm" star copolymers PS-b-PB2 (Run 11 (C),
Table 5-1), PS-b-PI2 (Run 12 (C), Table 5-1), and its precursor PS-(Br)2 (Run 2 (A),
Table 5-1). Conditions: [Li ] = 5x10-3 mOl.L^1, at R.T. in benzene.




























;1 h


75 7.0 65 6.0 55 5.0 45 4.0 35 3.0 25 2.0 1.5 1.0 0.5
8 (ppm)


Figure 5-30. 1H NMR spectrum (CD2C 2; 400 MHz) of an asymmetric star polybutadiene PB-b-
PB2(OH)2 (Run 10, Table 5-1).












i) s-BuLi -
Benzene, R.T., 20nun _


+ 4:


ii) TMEDA, R.T., 20lmin
iii) Styrene, R.T., 2h
iv) Ethylene oxide H
v) CH30H
PSG1(OH)
DH


: multifunctional core
O : branching points
S: PS chains


vi) DP19K
vii) 4,4 '-dibromodiphenyl ethylene ,
viii) CH,0H
THF, R.T.


vi)-viii)


i)-- v)


PSG2(OH)E


Figure 5-31i. Synthesis of third-generation dendrimer-like polystyrene.


































214









.' Tetmfunctiona
PSG-1Br IIPSG-1 in~itiar









Flow
marer




lil I I I l"I l"I II lil I
28 30 32 34 36 38 40 42 44 46 48 50 52
Elation time (mind


Tetmfunctiona
PBG-1Br i PBG-1 in~itiaor






Flowl
madr





lillliIIIII''l'l'''l'l
33 32 34~ 36 40 42 44 45 48 93

Elution time (min)

Figure 5-32. SEC traces (RI detector) of PS4(Br)s and PB4(Br)s aryl bromide-terminated
polystyrene and polybutadiene stars (Runs 2 and 28, Tables 5-2 and 5-3) and its
precursors (PS-OH)4 and (PB-OH)4 hydroxyl-terminated polystyrene and
polybutadiene stars (Runs 1 and 27, Tables 5-2 and 5-3) and the tetrabromoinitiator.



215








h e f b d
DH-H C,-H C-H, CH-CH2-OH
Hb t CH-CH 4H, c ~
HC


7.5 7.0 6.5 690 5.5 5J 4.5 41 35 3.0 25 2.0 15 1.0 0.5

8 (ppm)


Figure 5-33. 1H NMR spectrum (CD2 12; 400 MHz) of (PB-OH)4 hydroxyl-terminated
polybutadiene star (Run 27, Table 5-3).


a 8 b l e d
-CH2-CHCH-CH=CH--CH2i, CH2 CH2- O- CH2
,- d f


75 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 190 0.5

8 (pp m)


Figure 5-34. 1H NMR spectra (CD2 12; 400 MHz) of PB4(Br)s aryl bromide-terminated
polybutadiene star (Run 28, Table 5-3).



















































5 6 7 8 9 1011 1213141516171819
Elution time (min)

Figure 5-35. SEC traces (RI detector) of dendrimer-like polystyrenes (Runs 14, 16, 18, 20, 22,
24, and 26, Table 5-2). Conditions: [TMEDA]/[-PhLi] = 2, at R.T., in benzene.


217




























6 8 10 12 14 16 18 20 22 24 26 12 14 16 18 20 22 24 26
Elution time (min) Elution time (min)


Figure 5-36. SEC/HT traces (RI detector) of (A) dendrimer-like polystyrenes (Runs 14, 16, 18,
20, 22, 24, and 26, Table 5-2) and (B) dendrimer-like polybutadienes (Runs 27, 29,
and 31, Table 5-3). Conditions: [TIVEDA]/[-PhLi] = 2, at R.T., in benzene.






















b


6.0 5.5


8 (ppm)


Figure 5-37. 1H NMR spectrum (CD2C 2; 400 MHz) of a hydroxyl-terminated dendrimer-like
polybutadiene PB4-b-PBs(OH)s (Run 29, Table 5-3).






















































7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
8 (ppm)


Figure 5-38. 1H NMR spectrum (CD2 12; 400 MHz) of a aryl bromide-terminated dendrimer-like
polybutadiene PB4-b-PBs(Br)16 (Run 30, Table 5-3).



























2 3 4 5 6


Number of generation


Figure 5-39. Evolution of the hydrodynamic radius (RH) aS a function of the number of
generation (G) for dendrimer-like polystyrenes prepared using tetrafunctional (Runs
14, 16, 18, 20, 22, 24, and 26, Table 5-2).


-
1.4

-
1.3

-
1.2

1.1

1-


01


Figure 5-40. Evolution of Log[r] as a function of the number of generation (G) for dendrimer-
like polystyrenes prepared using tetrafunctional (Runs 14, 16, 18, 20, 22, 24, and
26, Table 5-2).


Numbe~r of generation











-
1.4

-
1.3


1.2 -

-
1.1

-
1


0.9 -1


0.8 -

0.5


Log Mn (x103 g.mol ')


Figure 5-41. Evolution of Log[r] as a function of Log Mn for
prepared from tetrafunctional (Runs 14, 16, 18, 20, 22,


dendrimer-like polystyrenes
24, and 26, Table 5-2).

















Mn x 10-3(g.mO -1) Mw SEC/LS Functionalitya
Run Type x 10-3 Mw n

theo SEC 1H NMR (mo-)theor OH PhBr


Table 5-1. Characteristics of asymmetric and "miktoarm" star (co)polymers.


PS-OH

PS-(PhBr)2

PEO-OH

PEO-(Br)2

PB-OH

PB-(PhBr)2

(PS)-b-(PS)2(OH)2

(PS)-b-(PS)2(OH)2

(PS)-b-(PS)2(OH)2

(PB)-b-(PB)2(OH)2

(PS)-b-(PB)2(OH)2

(PS)-b-(PI)2(OH)2

(PB)-b-(PS)2(OH)2


2.4

2.8

1.1

1.4

3.0

3.4

6.0

27.8

30.0

17.8

30.0

12.5

51.0


2.4

2.7

1.0

1.3

3.1

3.5

3.9

21.0

24.5

9.7

19.7

9.6

47.0


1.04

1.06

1.05

1.06

1.03

1.0

1.06

1.03

1.02

1.04

1.01

1.05

1.04


1.0 1.0


6.2

28.2

31.8

18

30.4

12.7

52.2


1.9

1.8 b

1.8 b

1.8

1.9b

1.9

1.9b


12.8

51.8


a Estimated by 1H NMR spectroscopy. b Estimated by titration of the hydroxyl end groups by DPMK ([DPMK] = 0.521 mol.L1


223














Mn x 10-3(g.mO -1) Functionalitya
Run Type MJ~Mn [7 9'b
(d L/g)
theor SEC SEC/HT theor OH PhBr


Table 5-2. Characteristics and solution properties of dendrimer-like polystyrenes.


PSG-1

PSG-1 Br

PSG-2

PSG-2Br

PSG-3

PSG-3Br

PSG-4

PSG-4Br

PSG-5

PSG-5Br

PSG-6

PSG-6Br

PSG-7


8.0

9.4

55.9

58.6

151.0

156.4

373.6

384.4

695.3

716.9

1212.5

1255.7

1822.0


3.08

4.3

40.3

41.7

91.2

95.6

189.9

198.5

363.3

382.3

586.0

628.2

610.4


7.9

9.3

57.0

59.4

153.6

158.9

375.3

387.4

710.5

730.6

1301.0

1345.4

1920.2


1.1

1.1

1.07

1.1

1.08

1.1

1.05

1.07

1.04

1.08

1.04

1.08

1.04


4

8

8

16

16

32

32

64

64

128

128

256

256


0.0608 0.84



0. 1848 0.63



0.2218 0.374



0.2156 0. 193



0.2047 0.116



0. 1679 0.062



0. 1228 0.034


15.8


15.90



31.8 c



64.7 c



127.7 c



255.6 c


31.8



64.1


127.0


255.0


a Estimated by 1H NMR spectroscopy. b g' = dendri linearr
groups by DPMK ([DPMK] = 0.521 mol.L^)~.


; ([r] = 1.23 x 10-2 Mno.71. c Estimated by titration of the hydroxyl end


224
















Mn x 10-3(g.mO -1) Functionalitya
Run Type MJ~Mn 91]'b

theor SEC SEC/HT theor OH PhBr


Table 5-3. Characteristics and solution properties of dendrimer-like polybutadienes.


PBG-1

PBG-2

PBG-2-Br

PBG-3

PBG-3-Br


14.0

36.7

41.3

121.9

135.0


7.6

28.4

29.0

72.6

74.0


14.5

38.6

41.9

129.6

131.4


1.03

1.05

1.05

1.05

1.05


15.8


15.7 c


31.7


Estimated by 1H NMR spectroscopy. b g' = dendri linearr ; ([9]
groups by DPMK ([DPMK] = 0.521 mol.L )~.


1.23 x 10-2 Mno.71. c Estimated by titration of the hydroxyl end


225









CHAPTER 6
CONCLUSION AND PERSPECTIVES



We have seen (Chapter 1) that in polymer chemistry polylithiation has never been

really contemplated, the main reasons held responsible for polylithiation to be impractical being

the secondary reactions occurring during the preparation of the polylithiated species and their

limited solubility in most organic solvents, forming rather insoluble aggregates of little utility.

We proposed here an entire set of hydrocarbon-soluble polycarbanionic initiators and

macroinitiators synthesized by using a simple halogen-lithium exchange reaction (Gilman's

reaction) carried out on multibromo molecule and macromolecule precursors. Using these

multicarbanionic (macro)initiators an entire set of complex polymer architectures have been

synthesized by anionic polymerization using a divergent method.

This strategy was first applied on multihalide molecules for the preparation of polymer

architectures such as SBS triblock copolymers with excellent mechanical properties, obtained

from a new hydrocarbon soluble (additive-free) dicarbanionic organolithium initiator containing

a side Cls-alkyl chain, or (PS),,, (PB);,, P(B-b-EO);, and P(S-b-B-b-M), (n = 3 or 4) star

(co)polymers obtained from tri- and tetracarbanionic initiators.

In a second instance, the Gilman reaction was extended on m,o'-dibromo chain-end

polymers after the introduction of a branching agent whose halogen atoms are carried by separate

aryl rings to afford hydrocarbon-soluble polycarbanionic macroinitiators. This provided an

efficient synthetic route to the asymmetric and "miktoarm" star (co)polymers based on the

combination of different polymers such as polystyrene, polybutadiene, and polyisoprene. By the

reiteration of this sequence of reactions (branching and halogen-lithium exchange reactions)









starting from a tetrafunctional initiator, dendrimer-like PS and PB up to the seventh and third

generations, respectively, could be successfully synthesized.

After demonstrating that a long side alkyl chain helps to solubilization of polylithiated

species, a new tetrafunctional initiator (Figure 6-1) containing long side alkyl chains, and thus

soluble in apolar solvents without any additives can be contemplated. Therefore, polydiene star

(co)polymers with a high percentage of 1,4-microstructure polybutadiene could be synthesized.

Moreover, all the previous results obtained let us hope that the same halogen-lithium

exchange reaction can be applied to linear chain polymers containing pendant aryl bromide

groups for the synthesis of more complex macromolecular architecture such as brush

(co)polymers (Figure 6-2).

We have also demonstrated that (PB-b-PEO)4 Star block copolymer could be used for the

synthesis of two-dimensional polymeric nanomaterials consisting of a continuously cross-linked

polybutadiene two-dimensional network with poly(ethylene oxide) domains of controlled sizes

trapped within the PB network. To reach that goal, novel (PB(Si(OEt)3)-b-PEO)3 Star block

copolymers were designed by hydrosilylation of the pendant double bonds of (PB-b-PEO)3 Star

block copolymer precursors with triethoxysilane. Self-condensation of the triethoxysilane

pendant groups under acidic conditions led to a successful cross-linking of the polybutadiene

blocks directly at the air/water interface without any additives or reagents.

The characterization of these 2D amphiphilic cross-linked materials should be

investigated (permeability, small angle scattering, and 2D viscometry) to understand the benefits

provided by 2D self-assembly at the air/water interface over conventional solution self-assembly

and other processes. In addition, such copolymer silanes monolayer could be easily transferred

and grafted through covalent bonds to inorganic surfaces (glass support such as silicon wafer) for







































i) s-BuLi

ii) Polymerization of
the monomer


polymer/inorganic composite synthesis. It could be also interesting to introduce triethoxysilane

groups, and other metal alkoxides on other polydiene block copolymers of more complex

architectures such as P(S-b-B-b-EO) triblock copolymers with the aim of stabilizing other

original 2D and 3D morphologies.


Figure 6-1. Conceivable tetracarbanionic initiator.


Figure 6-2. Synthetic strategy proposed for brush polymer preparation.









CONCLUSION ET PERSPECTIVES


Dand le premier chapitre, nous avons insisted sur le fait que les especes plurilithiees ont

ete tres peu utilisees dans le domaine de la chimie des polymeres. La presence de reactions

secondaires durant la preparation de ces especes plurilithiees et leur solubility limitee dans la

plupart des solvants organiques, formant plut8t des agregats insolubles peu utiles, en sont les

raisons principles.

Nous avons montre dans cette etude qu'il etait possible de preparer toute une nouvelle

famille d'amorceurs et macroamorceurs pluricarbanioniques soluble en solvant apolaire en

utilisant une reaction simple d'echange halogene-lithium (reaction de Gilman) a partir de

precurseurs halogenes moleculaires et macromoleculaires. L'utilisation de ces (macro)amorceurs

multicarbanioniques a permi s la synthese de toute une panoplie d' architectures

macromoleculaires complexes par polymerisation anionique par voie divergente.

Cette strategie a tout d'abord ete appliquee a des molecules multihalogenees pour la

synthese d'architectures polymeres tels que des copolymeres triblocs SBS a haute performance

mecanique, obtenus a partir d'un amorceur dicarbanionique soluble en sovant apolaire sans

additif, ou des (co)polymeres en etoile a base de differents monomeres (styrene, butadiene,

oxyde d'ethylene et methacrylate de methyle) a partir d'amorceurs tri- et tetracarbanioniques

solubles en milieu apolaire.

Dans un deuxieme temps, la reaction de Gilman a ete etendue a des chaines polymeres

divalentes (,o'-dibromees) apres introduction d'un agent de branchement compose de deux

noyaux aromatiques halogenes amenant ainsi a des macroamorceurs pluricarbanioniques soluble

en milieu apolaire. L'utilisation de ces derniers a permis la synthese de (co)polymeres en etoile










assymmetriques et << miktoarm >>, issues de differents monomeres tels le styrene, le butadiene ou

l'isoprene. La repetition de cette mime sequence de reactions (introduction d'un agent de

branchement et reaction d'echange halogene-lithium) a partir d'un amorceur tetracarbanionique a

aussi amene a la preparation de dendrimeres de polystyrene et polybutadiene de septieme et

troisieme generations, respectivement.

Apres avoir fait la demonstration de l'influence d'une longue chaine alkyle sur la

solubility des especes plurilithiees, nous pouvons tout a fait envisager la preparation d'un nouvel

amorceur tetracarbanionique possedant de longues chaines alkyles en position oc (Figure 5-42),

permettant ainsi leur solubilisation en milieu apolaire sans ajout d'additif. Cette strategie

permettrait alors la preparation de copolymeres en etoile a base de polydienes a haut taux

d'unites 1,4.

D'autre part, les differents resultats prealablement obtenus nous laissent esperer

l'application de la mime reaction d'echange halogene-lithium sur des chaines polymeres

possedant un groupement aromatique halogene sur chaque unite monomere permettant ainsi la

synthese possible d'architectures plus complexes tels que des (co)polymeres en peigne (Figure 5-

43).

Nous avons pu aussi demontrer au course du Chapitre 4 l'interit des copolymeres a blocs

en etoile (PB-b-PEO)4 dans le cadre de la synthese de nanomateriaux polymeres bidimensionnels

a base d'un reseau bidimensionnel de polybutadiene reticule constitute de domaines de

poly(oxyde d'ethylene) de tailles contr81es au sein du reseau. Pour atteindre cet objectif, un

copolymere a blocs en etoile silyle (PB(Si(OEt)3)-b-PEO)3 a ete prepare par hydrosilylation des

doubles liaisons pendantes du precurseur etoile (PB-b-PEO)3 CH preSence de triethoxysilane. La

condensation des groupements pendants triethoxysilane sous conditions acides a ainsi amene a la










articulation des blocs de polybutadiene directement a l'interface air/eau sans ajout d'additifs ou

reactifs.

Il serait maintenant interessant d'etudier plus en profondeur ce materiau amphiphile

reticule en deux dimensions a travers des techniques de caracterisation telles que la permeabilite,

la diffusion aux petits angles et la viscosimetrie bidimensionnelle pour ainsi mieux comprendre

l'interit de l'auto-assemblage en deux dimensions. D'autre part, il est tout a fait envisageable de

transferer et greffer a travers des liaisons covalentes de telles monocouches de copolymeres

silyles sur des supports inorganiques (silicon wafer) pour la preparation de materiaux

composites. Enfin, il serait interessant d'appliquer la mime strategie a d'autres copolymeres a

base de dines tels que les copolymeres triblocs P(S-b-B-b-EO) avec pour obj ectif la retention de

nouvelles morphologies bi- et tridimensionnelles.


Figure 6-1. Amorceur tetracarbanionique envisageable.












i) s-BuLi


\ n ii) Polymerization of
the monomer







Br



Figure 6-2. Strategie de synthese proposee pour la synthese de polymeres en peignes.









CHAPTER 7
EXPERIMENTAL PART

7.1 Purification of Reactants

The living anionic polymerization process requires, for their good unfolding, high purity

experimental conditions. For this purpose, all the polymerizations were run in glassware sets

equipped with teflon faucets and flame-dried under vaccum. All the chemicals needed for the

polymerization (solvents, monomers, additives) were beforehand purified, dried, and then

distilled under vaccum just before use. The different purification procedures for the solvents,

additives, and monomers are described in details below.

7.1.1 Solvents

Benzene (99%, J.T Baker), tert-butylbenzene (99%, Aldrich), toluene (99%, J.T Baker),

and cyclohexane (99%, J.T Baker) for polymerizations were dried and distilled twice over CaH2

and polystyryllithium, successively. THF (99%, J.T Baker) was purified by distillation over

CaH2 and then from a purple Na/benzophenone solution.

7.1.2 Initiators

All the multibromo precursors used for the pluricarbanionic initiators synthesis were

beforehand purified by lyophilization in benzene overnight.

7.1.3 Additives

Tetramethylethylenediamine (TMEDA) (Aldrich, 99%) was sodium-dried and distilled,

whereas 2-methoxy ethanol (Aldrich, 99%) was magnesium-dried and distilled.

7.1.4 Reactants for Halogen-Lithium Exchange and Deprotonation Reactions

Solutions of sec-Butyllithium (s-BuLi) (Aldrich) were used for halogen-lithium exchange

reaction after double titration.479 For the titration of s-BuLi, the following procedure was applied:

a 25 mL round-bottom flask fitted with a septum and containing a magnetic stirring bar was









evacuated and flushed with argon or nitrogen. Approximately 300 mg (1.56 mmol) of N-

pivaloyl-o-toluidine was charged into the flask. Anhydrous THF (10 mL) was added, and a white

sheet of paper was placed behind the flask. s-BuLi solution was then added dropwise until the

change in the color of the solution from colorless to yellow. Triplicate analyses were performed

in all cases.

The diphenylmethylpotassium (DPMK) solution, used for hydroxyl-deprotonation, was

prepared and titrated as described in the following procedures.462

Synthesis of diphenylmethylpotassium (DPMK). In a flame-dried 250 mL round-

bottom flask, pieces of potassium (4. 1 g, 0. 105 mol) were introduced followed by the addition of

dry THF (60 mL). Naphthalene (6.72 g, 5.25x10-2 mel) was added, turning the solution dark

green (due to the dissolution of potassium). The remaining THF (115 mL) was added along with

diphenylmethane (17.6 mL, 0.105 mol). All of these additions were performed under dry and

inert conditions. The resulting solution was stirred for one week and then used as such for the

anionic polymerization of ethylene oxide.

Determination of the concentration of DPMK. A flame-dried 100 mL round bottom

flask was charged with dry DMSO (10 mL) followed by a few grains (end of spatula) of

triphenylmethane. More DPMK was then added until the solution just turned red-orange.

Acetanilide (~0.2 g, 1.48x10-3 mel) was added, instantly turning the solution a clear light yellow.

The resulting solution was titrated with DPMK from a buret. Upon further addition of

acetanilide, the titration was repeated. Each addition and titration was carried out under dry and

inert conditions with the average concentration of DPMK determined be 5.162x10-4 mOl/mL.









7.1.5 Monomers

Styrene (S) (Aldrich, 99%) was dried and distilled under vacuum twice over CaH2 and

dibutyl magnesium successively. Butadiene (B) (Aldrich, 99%) was stirred over s-BuLi at -300C

for 2 h and distilled prior to use. Ethylene oxide (EO) (Fluka, 99.8%) was stirred over sodium

for 3 h at -40 oC and then distilled before use. Methyl methacrylate (MMA) (Aldrich, 99%) was

purified and distilled under vacuum twice over CaH2 and triethyl aluminium successively.

7.1.6 Terminating and Functionalization Agent

Diphenylethylene (Aldrich, 99%) used for the polybutadiene chain-end functionalization

was purified and distilled twice over CaH2 and s-BuLi successively.

Triethoxysilane (hydrosilylation agent) (Aldrich, 99%) and platinum(0)-1 ,3-divinyl-

1,1,3,3 -tetramethyldisiloxane complex (3 wt% solution in xylene) (Karstedt catalyst) (Aldrich,

99%), used for the hydrosilylation of the pendant polybutadiene double bonds, were employed as

received.

7.2 Preparation of Multibromo Precursors for Pluricarbanionic Initiator Synthesis

7.2.1 Synthesis of Dibromoprecursor for High Performance SBS Triblock Copolymers

Synthesis of 1-pentadecyl-3-phenoxy benzene. Into a two-neck round-bottom flask

fitted with a Dean and Stark apparatus equipped with a reflux condenser were placed 100 g (0.33

mol) of 3-pentadecyl phenol, 22.06 g (0.39 mol) potassium hydroxide, 300 mL of N,N-

dimethylacetamide and 150 mL of toluene. The reaction mixture was refluxed for 7 h with

continuous removal of by-product water. After completion of the reaction, the solvent was

distilled off and the obtained potassium salt of 3-pentadecyl phenol was dried under reduced

pressure. To a round bottom flask containing 111 g (0.32 mol) potassium salt of 3-pentadecyl

phenol were added 50.88 g (0.32 mol) of bromobenzene, 2.22 g Cu powder (2 wt % of potassium









salt of 3-pentadecyl phenol) and 150 mL of N,N-dimethylacetamide. The reaction mixture was

heated at 150oC for 8 h. The obtained dark colored reaction mixture was poured into 500 mL of

water and copper salts were removed by filtration. The filtrate was extracted with ethyl acetate (3

x 400 mL). The ethyl acetate solution was washed with water, followed by brine solution and

again with water and dried over sodium sulfate. Solvent evaporation yielded crude 1-pentadecyl-

3-phenoxy benzene. Pure 1 -pentadecyl-3-phenoxy benzene was obtained by silica gel (60-120

mesh) column chromatography (pet ether). Yield: 70 g (57 %). 1H NMR (CD2 12), 6 (ppm): 8.0-

6.5 (m, 9H1, ArH), 2.6 (m, 2H, -CH2-Ar), 1.7-1.0 (b, 26H, -CH2-CH3), 0.8 (m, 3H, -CH3).

Synthesis of 1-bromo-(4-bromophenoxy)-2-pentadecyl benzene. Into a three-neck

round-bottom flask equipped with a magnetic stirring bar, a reflux condenser, a dropping funnel

and a thermometer were placed 25 g (0.066 mol) 1 -pentadecyl-3-phenoxy benzene and 150 mL

dichloromethane. To the reaction mixture was added dropwise 22.08 g (0.14 mol) of bromine at

a temperature between -5 to 0 oC over a period of 15 minutes while the reaction mixture was

protected from light. After completion of bromine addition, the reaction mixture was stirred at

the same temperature for 1 h and then refluxed overnight. The excess bromine and hydrobromic

acid were neutralized with aqueous 10% NH3 (100 mL). The organic layer separated was washed

with water, followed by brine solution and again with water. The dichloromethane solution was

dried over sodium sulfate, filtered and the solvent was removed on a rotary evaporator. The

crude product was purified by silica gel (60-120 mesh) column chromatography to obtain pure 1-

bromo-(4-bromophenoxy)-2-pentadecyl benzene. Yield: 30 g (84%). 1H NMR (CD2 12),

6 (ppm): 8.0-6.5 (m, 7H, ArH), 2.6 (m, 2H, -CH2-Ar), 1.7-1.0 (b, 26H, -CH2-CH3), 0.8 (m, 3H, -

CH3) .









7.2.2 Synthesis of Tribromo Precursor

Synthesis of 1,3,5-tris(4-bromophenyl)benzene.211 To a solution of SmCl3 (0.5 mmol),

4-bromoacetophenone diethyl ketal (10 mmol) and pentane (15 mL), acetyl chloride (12 mmol)

was dropped under nitrogen atmosphere. After stirring for a proper time at room temperature, the

reaction was quenched by a mixture of benzene (20 mL) and H20 (10 mL). The organic layer

was separated and washed with the saturated aqueous solution of Na2CO3 and brine, dried over

anhydrous Na2SO4. COncentrated and recrystallized from n-hexane/dichloromethane, a needle

crystal was obtained (Yield = 60%). Melting point : 280.5-282.0 oC. 1H NMR (CDCl3),

6 (ppm): 7.8-7.5 (m, 15H, ArH). Anal. calc. for C24H15Br3 (%): C, 53.08; H, 2.78; Br, 44.14.

Found : C, 52.59; H, 2.55; Br, 43.67.

7.2.3 Synthesis of Tetrabromo Precursor

Synthesis of 1 ,3-bis(p-bromophenyl)-2-propane.21l2,213 Into a three-neck round-bottom

flask equipped with a distillation column, a mixture of 5 g (0.023 mol) of p-bromophenylacetic

acid and 1 g (0.024 mol) of magnesium oxide is heated up to 240 oC under vacuum during 5

hours to remove water formed during the condensation reaction. By heating up to 340 oC under

vacuum in a second instance, the targeted ketone is extracted by distillation. The crude product is

purified by recristallization in ethanol (Yield = 60 %). Melting point : 120-122 oC. 1H NMR

(CD2C 2), 6 (ppm): 7.5-6.9 (m, 8H, ArH), 3.7 (m, 4H, -CH2-C(= O)-).

Synthesis of 2,3,4,5-tetrakis(p-bromophenyl)-cyclopentainn.1,1,8,8 Into a

500 mL three-neck round-bottom flask equipped with a reflux condenser, 13 g (0.035 mol) of

compound A and 13 g (0.035 mol) of dibromobenzyle were dissolved in 250 mL of warm

ethanol and 100 mL of thiophene. Once the solution is refluxing (90 oC), a solution of 2 g of

potassium hydroxyde in 20 mL of ethanol is slowly added through the condenser. After 15









minutes refluxing, the reaction medium is dipped into an ice bath at 0 OC. The crude dark violet

product is recovered by filtration and then washed three times with 10 mL of ethanol (Yield = 70

%)>. 1H NMR (CD2C 2), 6 (ppm): 7.1 (d, 8H, Arll), 6.8 (d, 8H, Arll). Anal. calc. for C29H16Br40

(%): C, 49.75; H, 2.3; Br, 45.66; O, 2.29. Found : C, 49.65; H, 2.4; Br, 45.55; O, 2.4.

Synthesis of (1,2,3,4-tetrabromophenyl)-5-phenyl)benzen.1 Into atrenc

round-bottom flask equipped with a reflux condenser, 11 g (1.57x10-2 mel) of compound B, 0.89

g (8.72x10-3 mel) of phenylacetylene, and 4.2 g (2.3x10-2 mel) of benzophenone are dissolved in

100 mL of 0-dichlorobenzene. The reaction was carried out under reflux during three days.

During this time, the solution loses his violet color for a yellow color due to the carbon dioxide

emission. Once the reaction medium is cooled down to room temperature, 100 mL of methanol

were added to precipitate the tetrabromo compound. Recovered by filtration, the crude product

was then washed with methanol (Yield = 90%). 1H NMR (CD2 12), 6 (ppm): 7.1-6.5 (m, 22H,

Arll). Anal. calc. for (1,2,3,4-tetrabromophenyl)-5-phenyl)benzen (%): C, 55.85; H, 2.86; Br,

41.26; Found : C, 55.75; H, 3.06; Br, 41.19.

7.3 Preparation of a Branching Agent for Dendrimer-Like Synthesis

Synthesis of 4,4' -dibromodiphenylethylene. In a flamed and vacuum dried three-neck

flask equipped with a condenser and an additional funnel, 5 g (1.47x10-2 mO1) Of

dibromobenzophenone was dissolved in 40 mL of dry THF. 13 mL (1.82x10-2 mO1) Of

methylmagnesium bromide solution (1.4 M in toluene/THF (75:25)) were added dropwise to the

colorless solution. After the addition, the reaction medium became gray and the reaction was

stirred at 80 oC overnight. At the end of the reaction, the yellow reaction mixture obtained was

concentrated on a rotary evaporator to give 4.9 g of yellow cristals corresponding to the

intermediate 4,4' -dibromodiphenylethanol (Yield = 98 %). By dehydration of 4.9 g of 4,4'-









dibromodiphenylethanol warmed up to 180 OC, 4.65 g of a brown solid corresponding to the

4,4' -dibromodiphenylethylene (Yield = 95 %). 1H NMR (CD2C 2), 6 (ppm): 4,4'-

dibromodiphenylethanol : 7.5-6.7 (m, 8H, aromatic), 2.3 (s, 1H, -C(CH3)-OH), 1.8 (s, 3H, -

C(CH3)--OH). 4,4' -dibromodiphenyl ethyl ene: 7.5-6.7 (m, 8H, aromatic), 5.4 (s, 2H,

CH2= C(PhB r)2) -

7.4 Polymerization and Functionalization

7.4.1 Synthesis of High Performance Poly(styrene-b-diene-b-styrene) Triblock Copolymers

Polystyrene and polybutadiene telechelics preparation. In a flask, 145 mg (2.69x10-4

mol) of 1 -bromo-(4-bromophenoxy)-2-pentadecyl benzene were freeze-dried. 5 mL of

cyclohexane were added to make a precursor solution concentration of 5.3x10-2 mOl.L^1. 0.83 mL

(1.08x10-3 mel) of sec-butyllithium at a concentration of 1.3 M were added to the solution. After

20 minutes of reaction, the monomer was added dropwise. After the total consumption of the

monomer, an excess of ethylene oxide was added. The polymerization was deactivated by

degassed methanol. The linear polymer was precipitated using methanol. Dihydroxy-terminated

linear polybutadiene: 2r (SEC in THF) = 6,200 g/mol; 2v/2, = 1.13. 1H NMR (CD2 12),

6 (ppm): 8.0-6.9 (m, 7H, aromatic resonances from the difunctional initiator), 5.4 (m, 3H,-

CH2-CH=CH-CH2- and CH2=CH-CH-), 4.9 (s, 2H, CH2=CH-CH-), 3.6 (s, 4H, -

CH2-OH), 2.0 (b, 5H, -CH2-CH=CH-CH2- and CH2=CH-CH-), 1.2 (b, 2H,

CH2=CH-CH(R)-CH2-) 0.9 (b, 3H,-CH3).

Synthesis of SBS triblock copolymer. In a flask, 75 mg (1.39x10-4 mel) of 1-bromo-(4-

bromophenoxy)-2-pentadecyl benzene were freeze-dried. 3 mL of cyclohexane to obtain a

precursor solution at the concentration of 5.3x10-2 mOl.L^1 were introduced. 0.43 mL (5.56x10-4

mol) of sec-butyllithium at the concentration of 1.3 M was added to the solution. After 20









minutes of reaction, butadiene was added dropwise at 5 OC. After 24 hours of polymerization, the

reaction medium was diluted with a solution of cyclohexane/THF (100/1 in volume). Then

styrene was added and the color of the medium changed instantaneously from the characteristic

yellow color of polybutadienyllithium carbanions to the orange color of polystyryllithium

carbanions. The polymerization is let 12 hours at room temperature. Finally, the polymerization

is deactivated by degassed methanol. The triblock copolymer was precipitated in methanol. SBS

triblock copolymer: 2R ( H NMR in CDCl3) = 93,500 g/mol; 24/2 = 1.2. 1H NMR (CDCl3),

6 (ppm): 8.0-6.9 (m, 7H and 5H, aromatic resonances from the difunctional initiator and the

styrene units), 5.4 (m, 3H, --CH2--CH=CH--CH2-- and CH2=CH-CH-), 4.9 (s, 2H,

CH2= CH--CH--), 2.0 (b, 6H, --CH2--CH= CH--CH2--, CH2= CH-CH-, and Ar-

CH(R)-CH2-), 1.2 (b, 4H, CH2= CH--CH(R)--CH2-- and Ar--CH(R)--CH2-)>, 0.9 (b,

3H,-CH3).

7.4.2 Synthesis of Asymmetric and Miktoarm Star (Co)polymers

Synthesis of PS-OH and PB-OH hydroxyl-functionalized polymers. In a flamed and

vacuum dried three-neck flask, 1.55 mL (1.98x10-3 mel; [s-BuLi]o = 1.28 mol.L^1) were added on

30 mL of cyclohexane. 3.7 g of styrene was added and the color of the medium turned

instantaneously to the orange color of polystyryllithium carbanions. The polymerization was

allowed to proceed during 2 hours at room temperature and then end-capping was accomplished

by addition of a large excess of ethylene oxide. The reaction was deactivated by degassed acidic

methanol (3 mL of concentrated HCI in 50 mL of methanol). 1H NMR (CD2 12), 6 (ppm): PS-

OH (2R (SEC in THF) = 2,400 g/mol; 24/% = 1.04): 7.6-6.7 (m, 5H, aromatic), 3.6 (s, 2H, -

CH2-OH), 1.3-2.5 (m, 3H, Ar--CH(R)--CH2-- and Ar--CH(R)--CH2--), 0.7-1.1 (m, 3H,-

CH3 Of initiator). PB-OH (2A (SEC in THF) = 3,100 g/mol; 24/2 = 1.03): 5.4 (m, 3H, -










CH2-CH=CH-CH2- and CH2=CH-CH-), 4.9 (s, 2H, CE=-CH-CH-), 3.6 (s, 2H,-

CAz-OH), 2.0 (b, 5H, -CAz-CH=CH-CAz- and CH2=CH-CH-), 1.2 (b, 2H,

CH2=CH-C(R)H-CAz-), 0.7-1.1 (m, 3H, -CH3 Of initiator).

Synthesis of cu,w'-dibromo end-functionalized polymers. In a flamed and dried three-

neck flask, 1 g (3.22x10-4 mel) of PB-OH hydroxyl-terminated polybutadiene sample was freeze-

dried. The hydroxyl-terminated polybutadiene was first solubilized in 40 mL of THF, followed

by the addition of 0.62 mL (3.22x10-4 mel) of DPMK at a concentration of 0.521 mol.L^1. After

the titration of the hydroxyl end groups, the reaction medium became orange and then an excess

of 436 mg (1.29x10-3 mel) of freeze-dried 4,4'-dibromodiphenylethylene in solution in dry THF

were added to the mixture. The instantaneous reaction of potassium alkoxide living chain ends

on 4,4' -dibromodiphenylethylene give a purple violet solution. The reaction was deactivated by

addition of degassed methanol and concentrated on a rotary evaporator. The polymer was finally

precipitated using methanol to give 0.71 g of a crude product (71 %). 1H NMR (CD2 12), 6

(ppm): PS-(PhBr)2 (2 (SEC in THF) = 2,800 g/mol; 2y/2, = 1.06): 7.8-6.2 (m, 5H and 8H,

aromatic resonances from styrene units and chain end functions), 3.7 (s, 2H, -O-CH-

CH(PhBr)2), 3.4 (s, 2H, -CH-O-CH2--), 2.8 (m, 1H, -O-CH2-CH(PhBr)2), 1.3-2.5 (m, 3H,

Ar-CH(R)-CH2- and Ar--CH(R)--CH2-), 0.7-1.1 (m, 3H, -CH3 Of initiator). PB-

(PhBr)z 2 (SEC in THF) = 3,500 g/mol; 2y/2, = 1.04): 7.8-6.7 (m, 8H, aromatic), 5.4 (m, 3H,

-CH2-CH= CH-CH2- and CH2= CH-CH-), 4.9 (s, 2H, CE= CH-CH-), 3.7 (s, 2H, -

O-CH2-CH(PhBr)2), 3.4 (s, 2H, -CAz-O-CH2-), 2.8 (m, 1H, -O-CH2-CH(PhBr)2), 2.0 (b,

5H, --CH2-CH=CH--CH2- and CH2=CH-CH-), 1.2 (b, 2H, CH2=CH-CH(R)-CAz-)

0.7-1.1 (m, 3H, -CH3 Of initiator).










Synthesis of asymmetric and miktoarm star polymers. In a flamed and vacuum dried

three-neck flask, 150 mg (4.83x10-5 mol) of PB-(PhBr)2 aryl bromide-terminated precursor were

freeze-dried. The aryl bromide-terminated precursor was dissolved in 10 mL of dried benzene,

and then 0.15 mL (1.93x10-4 mel) of sec-butyllithium at a concentration of 1.3 M were added.

sec-Butyllithium was let to react with the aryl bromide end groups for 4 h to ensure the complete

lithium-halogen exchange reaction. A red-colored solution characteristic of the aryl lithiated

species was obtained at the end of the reaction. The monomer was added on the soluble

polylithiated species and the polymerization was allowed to proceed during 2 hours for styrene

and 24 hours for butadiene and isoprene. The end-capping of the living chain ends was

accomplished by addition of an excess of ethylene oxide. The reaction was deactivated by

degassed acidic methanol (3 mL of concentrated HCI in 50 mL of methanol). The reaction

mixture was concentrated on a rotary evaporator. The LiCl inorganic salts were removed by

extraction of a dichloromethane solution of the star polymer with distilled water. The polymer

solution was dried over sodium sulfate and concentrated. The star polymer was finally

precipitated using methanol. 1H NMR (CD2C 2), 6 (ppm): PB-b-PB2(OH)2 (M~w (SEC/LS in THF)

= 18,000 g/mol; Mw/Mn = 1.04): 7.8-6.2 (m, 8H, aromatic), 5.4 (m, 3H, --CH2--CH= CH--

CH2- and CH2=CH-CH-), 4.9 (s, 2H, CH2=CH-CH-), 3.7 (s, 2H, -O-CH2-CH(PhR)2),

3.4 (s, 10H, -CH2-O-CH2-, -CH2-OH and -CH(Ph-CH2-CH= CH-CH2-)2), 2.8 (m, 1H,-

O-CH2-CH(PhR)2), 2.0 (b, 5H, -CH2-CH=CH-CH2- and CH2=CH-CH-), 1.2 (b, 2H,

CH2=CH-CH(R)-CH2-) 0.7-1.1 (m, 3H, -CH3 Of initiator).


7.4.3 Synthesis of Star (Co)polymers

Synthesis of (PS-OH)n and (PB-OH)n (n = 3 or 4) hydroxyl-functionalized star-

shaped polystyrene and polybutadiene, G-1. In a flamed and vacuum dried three-neck flask,









50.1 mg (6.47x10-5 mol) of tetrabromoinitiator were freeze-dried. 12.2 mL of benzene were

added to make a precursor solution concentration of 5.3x10-2 mOl.L^1, followed by 0.122 mL

(1.55x10-3 mel) of 2-methoxy ethanol. 1.6 mL (2.07x10-3 mel) of sec-butyllithium at a

concentration of 1.3 M were added to the solution. After 20 minutes of reaction, butadiene was

added. The polymerization was allowed to proceed during 24 hours and then end-capping was

accomplished by addition of a large excess of ethylene oxide. The reaction was deactivated by

degassed acidic methanol (3 mL of concentrated HCI in 50 mL of methanol). The reaction

mixture was concentrated on a rotary evaporator. The LiCl inorganic salts were removed by

extraction of a dichloromethane solution of the star polymer with distilled water. The polymer

solution was dried over sodium sulfate and concentrated. The star polymer was finally

precipitated using methanol to give 1.04 g of a crude product (98 %). 2y (SEC/LS in THF) =

16,400 g/mol; 2y/2, = 1.05. 1H NMR (CD2C 2), 6 (ppm): 7.6-6.7 (m, 22H, aromatic resonances

from tetrafunctional initiator), 5.4 (m, 3H, -CH2-CH=CH-CH2- and CH2=CH-CH-),

4.9 (s, 2H, CH2=CH--CH--), 3.6 (s, 6H and 8H1 for the three- and four-armed star, -CH2-OH),

2.0 (b, 5H, --CH2-CH=CH--CH2- and CH2=CH-CH-), 1.2 (b, 2H, CH2=CH--CH(R)--

CH2-) -

P(styrene-b-butadiene-b-methyl methacrylate) star block terpolymer. In a flamed

and vacuum dried three-neck flask, 50. 1 mg (6.47x10-5 mol) of tetrabromoinitiator were freeze-

dried. 12.2 mL of benzene to obtain a precursor solution at the concentration of 5.3x10-2 mOl.L^1

and 0.122 mL (1.55x10-3 mel) of 2-methoxy ethanol were introduced. 1.6 mL (2.07x10-3 mO1) Of

sec-butyllithium at the concentration of 1.3 M were introduced. After 20 minutes of reaction,

styrene is added dropwise. After 2 hours of polymerization, butadiene was added at 5 OC and the

polymerization is let 24 hours at room temperature. Then an excess of diphenylethylene was









introduced to react with the polybutadienyllithium chain ends during 1 hour at 00C. The reaction

medium was diluted in 200 mL of tert-butylbenzene. Finally, methyl methacrylate was added

dropwise at -40 OC. After 1 hour, the polymerization was deactivated by degassed methanol. The

star block terpolymer was precipitated in methanol and purified by fractionation through a silica

gel column. P(SBM)4: 1 (1H NMR in CDCl3) = 16,100 g/mol; 2y/2, = 1.2. 1H NMR (CDCl3),

6 (ppm): 8.0-6.5 (m, 22H and 5H, aromatic resonances from the tetrafunctional initiator and the

styrene units), 5.4 (m, 3H, --CH2--CH=CH--CH2-- and CH2=CH-CH-), 4.9 (s, 2H,

CH2=CH--CH--), 3.5 (s, 3H, CH3-O-C(=0)--), 2.0 (b, 7H, --CH2--CH=CH--CH2- ,

CH2= CH-CH-, Ar-CH(R)-CH2-, and CH3-O-C(= O)-CH(R)-), 1.2 (b, 6H, CH2= CH--

CH(R)--CH2--, Ar--CH(R)--CH2--, and CH3-O-C(= O)-HR>-()CH2-) -

7.4.4 Synthesis of Dendrimer-Like Polymers

Synthesis of PS4-(PhBr)s and PB4-(PhBr)s o,o'-dibromo end-functionalized star-

shaped polystyrene and polybutadiene, G-1-Br. The PS4-(PhBr)s and PB4-(PhBr)s co,c'-

dibromo end-functionalized polystyrene and polybutadiene stars were synthesized according to

the same procedure previously described for the preparation of PS-(PhBr)2 and PB-(PhBr)2 aryl

bromide end-functionalized chain polymers. 1H NMR (CD2 12), 6 (ppm): PS4-(PhBr~s (2\M

(SEC/HT in dichlorobenzene) = 8,200 g/mol; 2y/2, = 1.1): 7.8-6.2 (m, 5H and 32H, aromatic

resonances from styrene units and chain end functions), 3.7 (s, 8H, -O-CH2-CH(PhBr)2), 3.4 (s,

8H, -CH2-O-CH2-), 2.8 (m, 4H, -O-CH2-CH(PhBr)2), 1.3-2.5 (m, 3H, Ar--CH(R)--CH2--

and Ar--CH(R)--CH2--). PB4-(PhBr)s (2r (SEC/HT in dichlorobenzene) = 15,200 g/mol;

1v/2, = 1.03): 7.8-6.6 (m, 22H and 32H, aromatic resonances from tetrafunctional initiator and

chain end groups), 5.4 (m, 3H, -CH2-CH=CH-CH2- and CH2=CH-CH-), 4.9 (s, 2H,

CH2=CH--CH-)>, 3.7 (s, 8H, -O-CH2-CH(PhBr)2), 3.4 (s, 8H, -CH2-O-CH2-), 2.8 (m, 4H,









-O-CH2-CH(PhBr)2), 2.0 (b, 5H, -CAz-CH=CH-CAz- and CH2=CH-CH-), 1.2 (b, 2H,

CH2= CH--CH(R)-CA,-) .

Synthesis of PS4-b-PSs(OH)s and PB4-b-PBs(OH)s hydroxyl-functionalized second-

generation dendrimer-like polystyrene and polybutadiene, G-2. In a flamed and vacuum dried

three-neck flask, 160.0 mg (1.95x10-5 mol) of PS4-(PhBr)s aryl bromide-terminated precursor

were freeze-dried. The PS4-(PhBr)s aryl bromide end-functionalized precursor was dissolved in

10 mL of dry benzene, and then 0.24 mL (3.12x10-4 mel) of sec-butyllithium at a concentration

of 1.3 M were added. sec-Butyllithium was let to react with the aryl bromide end groups for 4

hours to ensure the complete lithium-halogen exchange reaction. A red-colored solution

characteristic of the aryl lithiated species was obtained at the end of the reaction. At the end of

the halogen-lithium exchange reaction, 0.05 mL (2.28x10-3 mel) of TMEDA were added to the

reaction medium. After the solubilization of the polylithiated macroinitiator, the monomer was

added. The polymerization was allowed to proceed during 2 hours for styrene and 24 hours for

butadiene and then end-capping was accomplished by addition of a large excess of ethylene

oxide. The reaction was deactivated by degassed acidic methanol. The reaction mixture was

concentrated on a rotary evaporator. The LiCl inorganic salts were removed by extraction of a

dichloromethane polymer solution with distilled water. The polymer solution was dried over

sodium sulfate and concentrated. The dendrimer-like polymer was finally precipitated using

methanol. 1H NMR (CD2C 2), 6 (ppm): PS4-b-PSs(OH)s (2r (SEC/HT in dichlorobenzene) =

57,000 g/mol; 2y/2, = 1.07): 7.8-6.2 (m, 5H and 32H, aromatic resonances from styrene units

and chain end functions), 3.7 (s, 8H, -O-CH2-CH(PhR)2), 3.4 (s, 32H, -CHz-O-CH2- and -

CHz-OH), 2.8 (m, 4H, -O-CH2-CH(PhR)2), 1.3-2.5 (m, 3H, Ar-CH(R)-CH2- and Ar-

CH(R)--CH,-). PB4-b-PBs(OH)s (2\r' (SEC/HT in dichlorobenzene) = 38,600 g/mol; 2\y'/2\ =










1.05): 7.8-6.6 (m, 22H and 32H, aromatic resonances from tetrafunctional initiator and chain end

groups), 5.4 (m, 3H, -CH2-CH=CH-CH2- and CH2=CH-CH-), 4.9 (s, 2H, CH2=CH--

CH-), 3.7 (s, 8H, -O-CH2-CH(PhR)2), 3.4 (s, 24H, -CH2-O-CH2- and -CH2-OH), 2.8 (m,

4H, -O-CH2-CH(PhR)2), 2.0 (b, 5H, -CH2-CH= CH-CH2- and CH2= CH-CH-), 1.2 (b,

2H, CH2= CH--CH(R)--CH2- -

7.5 Two-Dimensional Cross-linking at the Air/Water Interface

7.5.1 Radical Cross-linking

Preparation of cross-linked (PB-b-PEO)3 star block copolymer monolayer with

AIBN. 100 CIL (C = Img/mL) of a chloroform solution of (PB200-b-PEO76)3 Star block copolymer

and 100 CIL (C = 0.2 mg/mL) of a chloroform solution of AIBN were spread dropwise with a

gastight Hamilton syringe on the Millipore water subphase. The chloroform was then allowed to

evaporate for 15 min to ensure no residual solvent remained. The subphase temperature was

maintained at 25 OC with water circulating under the trough. The monolayer was then

compressed up to a surface pressure of 20 mN/m with barrier compression speed of 5 mm.min l,

and the cross-linking reaction was carried out under UV light for 24 hours at 25 oC. For

photocross-linking, the Langmuir films were exposed to the radiation of a 80 W/cm medium

pressure mercury lamp, in the presence of air, at a passing speed of 50 m/min. At the end of the

reaction, the isotherm of the cross-linked monolayer was recorded after barrier expansion. The

cross-linked monolayer was removed from the water surface for FTIR study and transferred on a

mica substrate for AFM characterization.

7.5.2 Cross-linking by Self-condensation of Triethoxysilane Groups

Hydrosilylation of polybutadiene homopolymer. In a flamed and vacuum dried three-

neck flask equipped with a magnetic stirrer, a reflux condenser, a dry argon inlet and a heating









mantle, 142 mg (1.28x10-5 mol) of linear polybutadiene were freeze-dried and then dissolved in

20 mL of dried toluene. 0.573 mL (3.133x10-3 mel) of triethoxysilane and 0. 1 mL of the catalyst

platinum(0)-1,3-divinyl-1,1,3,3-tetramethydslxn complex (3 wt% solution in xylene) were

added, and the reaction was carried out under argon for 24 hours at 80 OC. At the end of the

reaction, the solvent and the nonreacted triethoxysilane were removed by evaporation under

vacuum and small samples were taken for NMR, and Langmuir trough studies. The product was

stored under dry argon (Crude product: Mn ( H NMR in CDCl3) = 33,500 g/mol; m = 135 mg).

1H NMR (6ppm; CDCl3): 5.4 (m, 3H, --CH2--CH=CH--CH2-- and CH2=CH-CH-), 4.9 (s,

2H, CH2= CH--CH--), 3.8 (s, 6H1, --CH2--Si(OCH2CH3)3), 2.0 (b, 5H, --CH2--CH= CH--

CH2- and CH2=CH-CH-), 1.5-0.9 (b, 11H, --CH2--Si(OCH2CH3)3, and CH2=CH--

CH(R)--CH2-), and 0.3-0.8 (s, 2H, --CH2--Si(OEt)3).

Preparation of crosslinked polybutadiene monolayers under acidic conditions. 100

CIL (C = Img/mL) of a chloroform solution of PB(Si(OEt)3) hydrosilylated polybutadiene were

spread dropwise with a gastight Hamilton syringe on the Millipore water subphase at pH = 3.0.

The monolayer was immediately compressed and hold at the desired surface pressure. The cross-

linking reaction was carried out for 10 hours at 25 OC to ensure a complete reaction and the

crosslinked monolayers were subsequently transferred onto mica substrate for further AFM

characterization. After cross-linking at 15 mN/m material initially formed could be with a spatula

after compressing the monolayer to a final area of ca 2 x 15 cm2, and was dried in a dessicator

for further FTIR study and solubility experiments.

Hydrosilylation of the (PB200-b-PEO326)3 Star block copolymer. In a flamed and

vacuum dried three-neck flask equipped with a magnetic stirrer, a reflux condenser, a dry argon

inlet and a heating mantle, 164 mg (2.17x10-6 mel) of (PB200-b-PEO326)3 Star block copolymer









were freeze-dried and dissolved in 15 mL of dry toluene. 0.285 mL (1.562x10-3 mO1) Of

triethoxysilane and 0.1 mL of the catalyst platinum(0)-1,3-divinyl-1,1,3,3-tetramethydslxn

complex (3 wt% solution in xylene) were added, and the reaction was carried out under argon for

24 hours at 80 OC. At the end of the reaction, the solvent and the unreacted triethoxysilane were

removed by evaporation under vacuum and small samples were taken for NMR, FTIR and

Langmuir trough studies. The product was stored under argon (Crude product: Mn ( H NMR) =

135,500 g/mol; m = 160 mg). 1H NMR (6ppm; CDCl3): 5.4 (m, 3H, --CH2--CH=CH--CH2--

and CH2= CH-CH-), 4.9 (s, 2H, CH2= CH-CH-), 3.8 (s, 6H, --CH2--Si(OCH2CH3)3), 3.6

(s, 4H, --CH2--CH2--O--), 2.0 (b, 5H, --CH2--CH= CH--CH2-- and CH2= CH-CH-), 1.5-

0.9 (b, 11H, --CH2--Si(OCH2CH3)3, and CH2=CH--CH(R)--CH2-), and 0.3-0.8 (s, 2H,-

CH2--Si(OEt)3)-

Preparation of cross-linked (PB(Si(OEt)3)-b-PEO)3 star block copolymer

monolayers under acidic conditions. 100 CIL (C = Img/mL) of a chloroform solution of

(PB(Si(OEt)3)-b-PEO)3 Star block copolymer were spread dropwise with a gastight Hamilton

syringe on the Millipore water subphase at pH = 3.0. The monolayer was immediately

compressed and hold at the desired surface pressure with barrier compression speed of 100

mm.min- The cross-linking reaction was carried out for 10 hours at 25 OC to ensure completion

of the reaction and the cross-linked monolayers were subsequently transferred onto mica

substrates for further AFM characterization. After cross-linking at 15 mN/m, the resulting

material could be removed with a spatula from the interface after compressing the monolayer to

a final area of ca 2 x 15 cm2, and was dried in a dessicator for further solubility studies.









7.6 Characterization Techniques


7.6.1 Elemental Analysis

The elemental analysis were carried out by Service Central d'Analyse of Vernaison (69-

France) .

7.6.2 Gas Chromatography

The chromatography set used is a Varian 350 equipped with a flame ionization detector

(FID).

Column characteristics :

Length : 15 m, internal diameter : 0.539 mm, non polar phase : dimethylsiloxane, film

thickness : 1.5 Clm, maximum temperature : 320 oC, and vector gas : He.

Analysis conditions :

Initial temperature : 35 oC during 2 minutes, final temperature : 240 oC (increase of 10

oC/min), Tinjector = 250 OC, Tdetector = 300 OC.

For the determination of the yield of the halogen/lithium exchange reaction in the case of

the pluricarbanionic initiators, the external standard method was preferred. The process is based

on the comparison of two chromatograms. For this purpose, a first reference solution of the

compound studied was prepared at a precise concentration Cref. A precise volume V of this latter

solution is inj ected and the area Arer of the peak corresponding to the compound studied. Then, a

same volume V of the sample containing the compound to titrate (concentration Csampl). In this

case, Asampl is the area of the corresponding peak. Because of the equal volume injected, the

areas Arer and Asample are prOportional, the area of each peak depending on the mass injected and

the corresponding concentration (mi = CiV).









For a precise adjustment of the apparatus, a linear relation exists for each peak between

the area of the peak and the amount of the corresponding compound in the sample inj ected. This

is valid for a range of concentrations depending on the type of detector used. This is expressed

by the following relation :

Mi = KiAi

where Mi is the mass of a compound i injected in the column, Ki is the absolute response

coefficient of compound i, and Ai is the area of the elution peak corresponding to the compound

i. This last expression applied on the on the chromatogram gives the following expression :

Cref = KAref and Csampl = KAsample Where (Csample) ref(Asampl/Arer)t.

For the kinetic studies, the internal standard method was used. This method is based on

the use of the relative response coefficient of each compounds to be titrated compared to the one

of an extra-compound introduced as a reference. This allowed to avoid the uncertainty due to the

inj ected volumes.

To select the internal standard it is necessary to get its elution peak well-defined (good

resolution) compared to the other peaks present on the chromatogram. Its retention time should

be close to the one(s) of the compounds) to be titrated. Its concentration should be higher or at

least close to the ones of the other compounds to get a linear response from the detector. Finally,

the internal standard should be inert towards the other compounds of the sample.

During the kinetic studies the following relation was used to determine the consumption

of the product studied :

% =[(Aproduct/Arer)t / (Aproduct/Arer)t=0] x 100

7.6.3 Size Exclusion Chromatography (SEC)

Apparent molar masses were determined with a size exclusion chromatography (SEC)

equipped with four TSK-gel columns (7.8 x 30 cm, 5 Clm, G 2000, 3000, 4000 and 5000 HR with









pore sizes of 250, 1,500, 10,000 and 100,000 A respectively) and THF as the mobile phase (1

mL/min). This instrument was equipped with a refractive index (RI) (Varian RI-4) and UV-vis

(Varian 2550 variable h) detectors. The SEC was calibrated using linear polystyrene samples.

Absolute molar masses of the different star polymers were calculated using a multiangle

laser light scattering (Photometer laser DAWV-F) detector (Wyatt Technology) connected to an

SEC line (abbreviated SEC/LS). The dn/dc values for the different stars were measured in THF

at 250C with a laser source operating at 633 nm (dn/dc = 0.183 cm3/g for the four-arm regular

and asymmetric polystyrene stars, 0.094 and 0.109 cm3/g for the four-arm regular and

asymmetric polybutadiene stars, respectively, and 0. 105, 0. 108, and 0.135 cm3/g for the (PS)-b-

(PB)2, (PS)-b-(PI)2, and (PB)-b-(PS)2 miktoarm star copolymers, respectively).

Absolute molar masses of the dendrimer-like polymer samples were determined with a

high temperature size exclusion chromatography (abbreviated SEC/HT in the following) using a

Waters 2000 CV SEC instrument, equipped with one column of HT 2 styragel and two columns

of HT 6E styragel and an online viscometric and refractive index detector, at 150 OC in

dichlorobenzene as solvent at a flow rate of 0.7 mL/min.

7.6.4 Nuclear Magnetic Resonance (NMR) Spectroscopy

1H NMR spectra were recorded on a Bruiker AC4000 and AC3000 spectrometer using

CDCl3, CD2 12 and CD30D as deuterated solvents. Chemical shifts are reported in ppm (6)

downfield from tetramethylsilane (TMS) and referenced to residual solvent.

To determine the 1,2- or 1,4-microstructures, the titration of two distinct peaks is used.

The first one at 5.4 ppm corresponds to the protons a and a' and the second one at 4.9 ppm to

the protons p as shown in the following scheme.











H2 H H2

CCCCCCH
H H2

HC




Based on the previous informations, we can write:

2x /(2y + x) = I(4.9) / I(5.4)

x +y =100

where x is the percentage of 1,2-structures, y is the one of 1,4-structures, and I(4.9) and

I(5.4) are the integration values corresponding to the peaks at 4.9 and 5.4 ppm.

7.6.5 Mass Spectrometry

Mass determination was carried out using an AutoSpec mass spectrometer

arranged in an EBE geometry (Micromass, Manchester, UK). The instrument

was operated at 8kV accelerating voltage in positive mode. The caesium

gun was set to 35 keV energy and 1 mL of sample was mixed in the tip of

the probe with a nitrobenzylalcohol matrix.

7.6.6 Viscometry

Viscometric measurements were performed in toluene at 35 OC using an Ubbelohde

viscometer (CT 52 Schott). The diameter of the capillar is 0.46 mm and the volume of the parent

solution is 15 mL (concentration : 250 mg in 15 mL). The capillar is dipped in a water bath at 35

oC. Samples were filtered through glass filters (200 Clm) before measurements.

From the flow time measured between two photodiodes for each polymer solution, [r]

value was determined by the traces of the two following straight lines :










rspe/C = f(C) and In neer/C = f(C) where Brel = T/To and rspe (r-r0) 90


The intersection of the two straight lines, at zero concentration, gives the intrinsic

viscosity of the polymer.

7.6.7 Infra-Red Spectroscopy

IR absorbance spectra were recorded on a Bruiker/Vector 22 FT/IR spectrometer. The dry

(co)polymers were solubilized in chloroform, and the solutions were subsequently spread

dropwise onto KBr pellets and allowed to dry in a dessicator.

7.6.8 Mechanical Properties Analysis

Samples were tested on an Instron Universal Testing machine (model 4466) in a

controlled environment room at 23 + 2 oC and 50 % of relative humidity. A 500 N static load cell

with self-aligning grips and stainless steel faces (Instron Corporation) was used. The tensile

measurements were performed with a cross-head speed of 10 mm/min and an initial grip

separation of 35 mm. Tensile properties (tensile strength and elongation at break) were

calculated with Series IX Automated Materials Testing System software (Instron Corporation).

The fi1ms had a thickness of approximately 0.75 mm, a width of 4 mm, and a gauge length of 40

mm (the mean thickness of each sample was performed with a Fowler micrometer). Five samples

from the same fi1m were tested for each copolymer.

7.6.9 Langmuir Films

Surface fi1m characterization was accomplished using a Teflon Langmuir trough (Width

= 150 mm and Length = 679 mm) system (KSV Ltd., Finland) equipped with two moving

barriers and a Wilhelmy plate for measuring surface pressure. Between runs, the trough was

cleaned with ethanol and rinsed several times with Millipore filtered water of ~ 18 MGZ.cm

resistivity. The subphase temperature was maintained at 25 OC through water circulating under









the trough. Samples were typically prepared by dissolving ~1 mg of copolymer in 1 mL of

chloroform and spread dropwise with a gastight Hamilton syringe on the Millipore water

subphase. For the surface property studies of the (PB-b-PEO)3 Star block copolymers, the

chloroform was allowed to evaporate for 30 min to ensure no residual solvent remained and the

isotherm and hysteresis experiments were run with barrier movement of 5 mm.min- The

compression/expansion cycles for the hysteresis experiments were repeated five times after a

delay of thirty minutes during which the monolayer was allowed to relax at n: = 0 mN.ml

Isotherm and hysteresis experiments were performed at least three times to verify

reproducibility. The data resulting from the isotherms (Ao, AA, and Apancake) Were plotted vs. the

number of EO units and fitted by a linear curve.

In the case of the (PB(Si(OEt)3-b-PEO)3 Star block copolymers, the isotherms were

recorded after different reaction times during cross-linking for various subphase pH values with

a barrier compression speed of 100 mm.min- The isobar experiments were carried out at a

surface pressure of 5 or 10 mN/m for different subphase pH values.

7.6.10 Atomic Force Microscopy

Surface films of the linear homopolymers and star (co)polymers were transferred onto

freshly cleaved mica at various pressures. The desired surface pressure was attained by a

continuous compression of 0.5 mN.m-l at rates of 10 mm.min- Once the film had equilibrated at

a constant n: for at least 15 minutes, the mica was then pulled at a rate of 1mm.min- The

transferred film was dried in a dessicator for 24 hours and subsequently scanned in tapping mode

with a Nanoscope III AFM (Digital Instruments, Inc. Santa Barbara, CA) using silicon probes

(Nanosensor dimensions: T = 3.8-4.5 Clm, W = 27.6-29.2 Clm, L = 131 Clm). Using Digital










Instruments software, the images were processed with a second order flattening routine while

size, height and number of domains were measured through section analysis.


Cu Powder

Br + K6 80 yield 57% a

CisH31


Figure 7-1. Synthesis of 1-pentadecyl-3-phenoxy benzene.


C15H31


EtO Oft



Br


acetyl chloride, SmCl3

pentane, R.T., 24h


Figure 7-2. Synthesis of 1,3,5-tris(4-bromophenyl)benzene.



MgO IO
Br H2OOH 2 o rCH--CH2 B

(A)

Figure 7-3. Synthesis of 1,3-bis(p-bromophenyl)-2-propane.


0 0 KOH/EtOH

/ EtOH / Thiophene
\ / 1100C
Br' Br


(A)


Figure 7-4. Synthesi sof 2,3,4,5 -tetraki s(p-bromophenyl)-cyclopentadienone .













- CO


+
O=H


Figure 7-5. Synthesis of (1 ,2,3,4-tetrabromophenyl)-5-phenyl)benzene


256










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BIOGRAPHICAL SKETCH

Rachid Matmour was born in Bordeaux, France, in 1978. After a brief stay in Bordeaux,

he grew up in Perigueux (Dordogne, France). Rachid received his B.S. in chemistry in 2000 and

his M.S. in polymer chemistry in 2002 from the University of Science and Technology of

Bordeaux 1, France. Also in 2002, he started a joint Ph.D. program working in both Dr. Yves

Gnanou's group at the Laboratoire de Chimie des Polymeres Organiques (LCPO) in the

University of Bordeaux 1, and Dr. Randolph S. Duran's group in the Center for Macromolecular

Science and Engineering at the University of Florida. With Dr. Yves Gnanou, he worked on the

synthesis of complex polymer architectures (block copolymers, star polymers, and dendrimer-

like polymers) by living anionic polymerization and controlled radical polymerization. With Dr.

Randolph S. Duran, he studied the surface active properties of amphiphilic star block copolymers

and their application for the synthesis of two-dimensional polymeric nanomaterials at the

air/water interface.





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1 APPLICATION OF LITHIUM/HALIDE EXCHANGE REACTIONS TO THE SYNTHESIS OF COMPLEX POLYMER ARCHITECTURES: INVESTIGATION OF THEIR SELFASSEMBLING PROPERTIES AT THE AIR/WATER INTERFACE By RACHID MATMOUR A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA AND THE UNIVERSITY OF BORDEAUX I IN PARTIAL FULFILLMENT OF THE RE QUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA UNIVERSITY OF BORDEAUX 1 2007

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2 Copyright 2007 Rachid Matmour

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3 To my parents and my brother thanks for everything.

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4 ACKNOWLEDGMENTS This dissertation is the result of 4 years of research between the Laboratoire de Chimie des Polymres Organiques (LCPO) at the Un iversity of Bordeaux 1 and the Center for Macromolecular Science and Engineering (Departm ent of Chemistry) at the University of Florida. Graduate school is one of the most difficult tim es in a persons life. During the time that I was engaged in this study, the life was some da ys nice because of the in teresting experimental results obtained after many hours, days, and m onths of work which made me proud, and more difficult some other days because of the experiment s that I had to repeat week after week until I fixed what was wrong. After these four years of re search, I can say for sure that graduate school teaches patience and perseverance. However, without the support of others I could not have achieved this seemingly insurmountable goal. First and foremost I would li ke to thank my parents, Houcine and Fettouma Matmour. They arrived in France in the 1970s from Morocco. Even if they are not really rich, they gave me something that one cannot buy: th eir love and guidance throughout my life. Their unwavering confidence has enabled me to conti nue when my efforts have fallen short, never doubting that the next try will be a successful on e. Their unconditional love is something that I have relied on regardless of th e time period or distan ce between us. I am proud to be their son, and I am proud to say that this is the foundation on which all else has been possible. I do not hesitate to say that I could not have complete d graduate school without them. Because of all these reasons, this dissertation is dedicated to my parents. With no less sincerity, I would also like to tha nk especially five persons for the impact each one has made on me as a scientist throughout my undergraduate and graduate school. First, I am extremely grateful for the assistance and advice I received from Prof. Yves Gnanou. Since the

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5 time I started my Ph.D. in 2002 under his supervis ion, I learned a lot fr om his experience. I greatly appreciate the time he ha s taken to enlighten me with his perspectives on science, writing, and the world of chemistry as it stan ds today. His experience d advice has been an integral part of my education and has given me a deeper understanding of what is needed to be successful as a research chemist. I also am grateful for the incred ible effort he has put forth to strengthen my research, and especially this doc ument. Finally, I would like to thank him for the good advice he gave me concerni ng my future after the Ph.D. I would like to thank Prof. Randolph Duran, w ho was my advisor at the University of Florida. First, without his help I would never have had the chance to spend two years at the University of Florida for this jo int Ph.D. program. This gave me the opportunity to be a Research Assistant in Prof. Durans group working on Langmuir and Langmuir-Blodgett films and a Teaching Assistant for Prof. Horvath for one year. I thank the students whom I was privileged to teach and from whom I also learned much, especi ally Stacey Gray (I will miss her!), Kathleen Evans, Natalie Nix, Alicia Kinsey, Ashley Holmes, Wilfredo Herrera, John Keenan, Ashley Dekleine, Leigh Klein, La uren Kelley, Tommasina Miller, and Erin McGuinn (I thank them for making Gainesville like my home!). Because of all these good experiences I had at the University of Florida, I am extrem ely grateful to Prof. Randolph Duran. I would like to thank Dr. Dani el Taton, Assistant-Professor at the LCPO, whom I met in 2001. He was my advisor during my pre-Ph.D. year During this time he first showed me the importance for a researcher to deeply study the lit erature before starting any experiments at the bench. I appreciated his real ly good experience in the area of macromolecular complex architectures and radical contro lled polymerization. Because of him, I really understood the

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6 interest of synthesizing differe nt kinds of polymeric architect ures and studying their properties and applications. My interest in this science comes from there! I owe a special note of gratitude to Dr. Eric Cloutet, CNRS Sc ientist at the LCPO, who first introduced me to the polymer sciences. I met him in March 2001 and worked on my undergraduate research under his supervision. Duri ng this period, he first showed me how to correctly and safely manipulate the experiments, but he was also the firs t one to show me the interests and applications of pol ymer chemistry. Because of him, I decided to focus on polymer chemistry and to study more deeply this science. Finally, I wish to thank my friend, Thomas Joncheray, for his collaboration on different projects. I met Emilie Galand (his girlfriend) and him for the first time in 2003 at the University of Florida. They helped me a lot concerning all the administrative affairs at the University of Florida (I thank Emilie, who is really the best!). Besides that, I had the chance to work with Thomas on the synthesis of two-dimensiona l polymeric nanomaterials, which gave two publications (that was a r eally good team!). Even if we were working very hard during the day, that was always with a good m ood in the lab, which helps work ing very late in the night. Because of the different events we shared in th e lab, I think we will remember our stay in Prof. Durans group for the rest of our life. Many people on the faculty and staff of the Gra duate School of the Univ ersity of Florida, the Center for Macromolecular Science and Engin eering, and the LCPO assisted me in various ways during my course of studies. I am especi ally grateful to Dr. Ben Smith, Lori Clark, Catherine Roulinat, Corinne Gonalves de Carv alho, Nicole Buzat, Bernad ette Guillabert, and Emmanuel Ibarboure.

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7 I extend many thanks to my colleagues and fr iends: David Lanson (the Globtrotter), the French Running Team of LCPO (Profs. Henri Cramail and Sbastien Lecommandoux, Dr. Daniel Taton, Dr. Eric Cloutet, Romain Perrier-Cornet, Nicolas Guidolin), Amli Baron (the most kindly girl), the basketba ll team of Gainesville (Thoma s Joncheray, Pierre Beaujuge, Benot Lauly, James Lonard, Christophe Grenier, Dimitri Hirsch-Weil), T homas Dalet (alias the Joker!), Jan Merna (alias Crazy Man), Renjith Devasia, the N1-33 team (Colonel Cloutet, Anne de Cuendias, Ccile Bouilhac, Pierre Chambon). I would also like to thank all th e people I have had the pleasure to meet during my stay at the Laboratoire de Chimie des Polymres Orga niques (University of Bordeaux 1) and at the Center for Macromolecular Science and Engineer ing (Department of Chemistry, University of Florida). Finally, the members of my dissertation committee, Lisa McElwee-White, Monique Mauzac, Eric Enholm, Ben Dunn, Georges Hadz iioannou, Daniel Taton, Randolph S. Duran and Yves Gnanou, have generously given their time a nd expertise to better my work. I would like to thank them for their judgment and their contribution to this work.

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8 TABLE OF CONTENTS page ACKNOWLEDGMENTS...............................................................................................................4 LIST OF TABLES................................................................................................................. ........12 LIST OF FIGURES................................................................................................................ .......13 ABSTRACT....................................................................................................................... ............21 CHAPTER 1 POLYLITHIATED SPECIES: APPLIC ATION TO POLYMER SYNTHESIS...................25 1.1 Introduction............................................................................................................... ........25 1.2 By Reaction with Lithium................................................................................................25 1.3 By Reaction of Alkyllithium on Mu ltifunctional Unsaturated Molecules.......................26 1.4 By Lithium-Halogen Exchange Reaction.........................................................................28 1.5 By Reaction with a Base...................................................................................................3 1 1.6 Conclusion................................................................................................................. .......31 2 A NOVEL ADDITIVE-FREE DICARBANIONIC INITIATOR FOR THE SYNTHESIS OF POLY(STYRENEb -DIENEb -STYRENE) TRIBLOCK COPOLYMERS IN NON-POLAR MEDIUM......................................................................35 2.1 Introduction............................................................................................................... ........35 2.2 Literature Overview on Symmet ric ABA Triblock Copolymers.....................................36 2.2.1 Sequential Monomer Addition...............................................................................36 2.2.2 Coupling of Living AB Chains...............................................................................37 2.2.3 Use of a Difunctional Initiator................................................................................39 2.2.3.1 Divinylbenzene derivatives..........................................................................40 2.2.3.2 Diphenylethylene-type molecules................................................................42 2.2.3.3 Use of alkali metals......................................................................................43 2.3 Results and Discussion..................................................................................................... 44 2.4 Conclusion................................................................................................................. .......48 3 TRIAND TETRACARBANIONIC INITIA TORS BY A LITHIUM/HALIDE EXCHANGE REACTION : APPLICATION TO STAR-POLYMER SYNTHESIS...........64 3.1 Introduction............................................................................................................... ........64 3.2 Literature Overview on (A)n and (AB)n Star Polymer Synthesis.....................................65 3.2.1 Arm-first Method................................................................................................65 3.2.1.1 Use of multifunctional coupling agent.........................................................66 3.2.1.2 Copolymerization with a divinyl compound................................................73 3.2.2 Core-first Method................................................................................................75 3.2.2.1 Multifunctional oxanionic initiators.............................................................76

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9 3.2.2.2 Pluricarbanionic initiators............................................................................77 3.2.2.3 Polythiolates initiators..................................................................................78 3.2.3 In-Out Method....................................................................................................78 3.2.4 In-In Method.......................................................................................................80 3.3 Results and Discussion..................................................................................................... 80 3.3.1 Application of Halogen-Lithium Ex change Reaction to Star Polymer Synthesis................................................................................................................80 3.3.2 Synthesis of Amphiphi lic Star Block Copolymer s Based on Polybutadiene and Poly(ethylene oxide).......................................................................................84 3.4 Conclusion................................................................................................................. .......87 4 TWO-DIMENSIONAL POLYMERIC NANOMATERIALS THROUGH CROSSLINKING OF POLYBUTADIENEb -POLY(ETHYLENE OXIDE) MONOLAYERS AT THE AIR/WATER INTERFACE..................................................................................106 4.1 Introduction and Literature Overview............................................................................106 4.2 Interfacial Behavior of (PBb -PEO)n (n = 3 or 4) Star Block Copolymers at the Air/Water Interface.........................................................................................................110 4.2.1 Surface Pressure-Area Isotherms.........................................................................112 4.2.2 Film Relaxation....................................................................................................114 4.2.3 AFM Characterization of the Transferred Monolayers........................................115 4.3 Cross-linking of Polybutadieneb -Poly(ethylene oxide) Monol ayers at the Air/Water Interface...................................................................................................................... ...118 4.3.1 Interfacial Behavior of (PBb -PEO)3 Star Block Copolymers.............................119 4.3.2 Reaction of the Polybutadiene Bloc k at the Air/Water Interface in the Presence of AIBN................................................................................................120 4.3.3 Cross-linking with Hydrosilylated Pol ybutadiene Blocks at the Air/Water Interface...............................................................................................................121 4.3.3.1 Application on polybutadiene homopolymer.............................................121 4.3.3.2 Application on (PBb -PEO)3 star block copolymer...................................126 4.4 Conclusion................................................................................................................. .....133 5 PLURICARBANIONIC MACROINIT IATORS BY A LITHIUM/HALIDE EXCHANGE REACTION : APPLICATION TO ASYMMETRIC AND MIKTOARM STAR AND DENDRIMER-LIKE POLYMER SYNTHESIS.............................................163 5.1 Introduction and Literature Overview............................................................................163 5.1.1 Asymmetric and Miktoarm Star Polymers.......................................................163 5.1.2 Dendrimer-like Polymers.....................................................................................167 5.1.2.1 Introduction to dendrimers.........................................................................167 5.1.2.2 Dendrimers with true macromolecular generations................................172 5.2 Results and Discussion...................................................................................................17 6 5.2.1 Synthesis of Asymmetric and Miktoarm Star Polymers......................................176 5.2.1.1 Introduction of the bran ching point at the chain end of a linear polymer..177 5.2.1.2 Preparation of pluricarbanionic macroinitiators for star polymer synthesis.....................................................................................................179 5.2.2 Synthesis of Dendrimer-Like Polystyrene and Polybutadiene.............................180

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10 5.2.2.1 Synthesis of star-shaped (G-1 ) polystyrene and polybutadiene precursors...................................................................................................180 5.2.2.2 Introduction of the branch ing points at each arm end................................182 5.2.2.3 Preparation of pluricarbanionic initiators for second generation (G-2) dendrimer-like polystyrene a nd polybutadiene synthesis..........................183 5.2.2.4 Third-generation (G-3) dendrimerlike polystyrene and polybutadiene....184 5.2.2.5 From the fourth(G-4 ) to the seventh-genera tion (G-7) dendrimer-like polystyrene synthesis.................................................................................186 5.2.2.6 Viscosity behavior of dendrimer-like polystyrenes...................................187 5.3 Conclusion................................................................................................................. .....189 6 CONCLUSION AND PERSPECTIVES..............................................................................226 7 EXPERIMENTAL PART....................................................................................................233 7.1 Purification of Reactants.................................................................................................2 33 7.1.1 Solvents................................................................................................................2 33 7.1.2 Initiators............................................................................................................... .233 7.1.3 Additives...............................................................................................................2 33 7.1.4 Reactants for Halogen-Lithium Exchange and Deprotonation Reactions............233 7.1.5 Monomers.............................................................................................................235 7.1.6 Terminating and Functionalization Agent............................................................235 7.2 Preparation of Multibromo Precursors fo r Pluricarbanionic Initiator Synthesis............235 7.2.1 Synthesis of Dibromoprecursor fo r High Performance SBS Triblock Copolymers..........................................................................................................235 7.2.2 Synthesis of Tribromo Precursor..........................................................................237 7.2.3 Synthesis of Tetrabromo Precursor......................................................................237 7.3 Preparation of a Branching Agent for Dendrimer-Like Synthesis.................................238 7.4 Polymerization and Functionalization............................................................................239 7.4.1 Synthesis of High Performance Poly(styreneb -dieneb -styrene) Triblock Copolymers..........................................................................................................239 7.4.2 Synthesis of Asymmetric and Miktoarm Star (Co)polymers...............................240 7.4.3 Synthesis of Star (Co)polymers............................................................................242 7.4.4 Synthesis of Dendrimer-Like Polymers...............................................................244 7.5 Two-Dimensional Cross-linking at the Air/Water Interface..........................................246 7.5.1 Radical Cross-linking...........................................................................................246 7.5.2 Cross-linking by Self-condensa tion of Triethoxysilane Groups..........................246 7.6 Characterization Techniques..........................................................................................249 7.6.1 Elemental Analysis...............................................................................................249 7.6.2 Gas Chromatography............................................................................................249 7.6.3 Size Exclusion Chromatography (SEC)...............................................................250 7.6.4 Nuclear Magnetic Resonance (NMR) Spectroscopy............................................251 7.6.5 Mass Spectrometry...............................................................................................252 7.6.6 Viscometry...........................................................................................................252 7.6.7 Infra-Red Spectroscopy........................................................................................253 7.6.8 Mechanical Properties Analysis...........................................................................253 7.6.9 Langmuir Films....................................................................................................253

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11 7.6.10 Atomic Force Microscopy..................................................................................254 LIST OF REFERENCES............................................................................................................. 255 BIOGRAPHICAL SKETCH.......................................................................................................281

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12 LIST OF TABLES Table page 2-1 Characterization of PS and PB samples synthesized from 1 difunctional initiator................62 2-2 Mechanical properties of SBS triblock copolymers initiated by 1 .........................................63 3-1 Characterization of PS and PB samples synthesized from 1 2 and 3 initiators, respectively................................................................................................................... .........103 3-2 Characterization of P(Sb -Bb -M)2 pentablock, P(Sb -Bb -M)3 and P(Sb -Bb -M)4 star block terpolymer samples......................................................................................................1 04 3-3 Characteristics of hydroxyl functionalized (PB-OH)n star polymers and (PBb -PEO)n (n = 3 or 4) amphiphilic star block copolymers.........................................................................105 4-1 Measurements obtained from isotherm experiments of (PBb -PEO)4 amphiphilic star block copolymers............................................................................................................... ....160 4-2 Characteristics of LB film experiments.................................................................................161 4-3 AFM characteristics of (PBb -PEO)4 four-arm star copolymers...........................................161 4-4 Data for (PBb -PEO)3 and (PB(Si(OEt)3)b -PEO)3 star block copolymers..........................162 5-1 Characteristics of asymmetric an d miktoarm star (co)polymers.......................................223 5-2 Characteristics and solution proper ties of dendrimer-like polystyrenes...............................224 5-3 Characteristics and solution proper ties of dendrimer-like polybutadienes...........................225

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13 LIST OF FIGURES Figure page 1-1 Wurtz coupling reaction.................................................................................................... ......33 1-2 Synthesis of a tric arbanionic initiator.................................................................................... ..33 1-3 Synthesis of polylithiated carbosilane dendrimers..................................................................33 1-4 Synthesis of pluricarba nionic species from DVB....................................................................34 1-5 Halogen-lithium exchange reaction.........................................................................................3 4 1-6 Synthesis of a dicarbanionic init iator from a dibromo precursor............................................34 2-1 Synthesis of SBS tribock copolym er by sequential monomer addition..................................49 2-2 Synthesis of SIS triblock copol ymer by coupling of living chains on dichlorodimethylsilane......................................................................................................... ....49 2-3 Synthesis of P(Sb t BAb -S) triblock copolymer by c oupling of living chains on bis(bromomethyl)benzene........................................................................................................ 50 2-4 Synthesis of SBS triblock copolymer us ing 1,3-diisopropenylbenzene as precursor.............50 2-5 Synthesis of SBS triblock copolymer using 1,3-di(1-phenylethenyl)benzene as precursor...................................................................................................................... ............50 2-6 Complex diolefinic precurs ors used for the synthesis of organolithium diinitiators...............51 2-7 Synthesis of SBS triblock copolymer fr om a dicarbanionic initiator formed by the reaction of lithium metal and -methylstyrene........................................................................52 2-8 Synthesis of P(EOb -Ib -EO) triblock copolymer from a difunctional initiator formed by the reaction of potassium metal and naphtalene......................................................................52 2-9 Synthesis of 1-bromo-4-(4-bromophenoxy )-2-pentadecyl benzene ( 1 ).................................53 2-10 1H and 13C NMR spectra (CD2Cl2, 400 MHz) of 1-bromo-4-(4-bromophenoxy)-2pentadecyl benzene ( 1 ).........................................................................................................54 2-11 Mass spectrum of 1-bromo-4-(4-bro mophenoxy)-2-pentadecyl benzene ( 1 )......................55 2-12 Synthesis of a dicarbanionic initiator by halo gen-lithium exchange reaction using 1 as dibromo precursor.............................................................................................................. ...55 2-13 Secondary reactions resulting from th e halogen-lithium exchange reaction.........................56

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14 2-14 1H and 13C NMR spectra (CD2Cl2, 400 MHz) of the addition product of 1 with sec butyllithium obtained after methanolysis..............................................................................57 2-15 Mass spectrum of the addition product of 1 with sec -butyllithium obtained after methanolysis................................................................................................................... ......58 2-16 Synthesis of -dihydroxy telechelic polybutadiene from 1 ..............................................58 2-17 SEC eluograms of (PS)2 difunctional polystyrene and (PB)2 difunctional polybutadiene....59 2-18 1H NMR spectrum (CD2Cl2, 400 MHz) of -dihydroxy terminated polybutadiene.........60 2-19 13C NMR spectrum (CDCl3, 400 MHz) of a -dihydroxy terminated polybutadiene.......60 2-20 Synthesis of SBS triblock copolymer from 1 .......................................................................61 2-21 SEC eluograms monitoring the formation of a SBS triblock copolymer initiated in cyclohexane with 1 ..............................................................................................................61 2-22 1H NMR spectrum (CDCl3, 400 MHz) of a SBS triblock copolyme.....................................62 3-1 General strategies for star polymer synthesis..........................................................................88 3-2 Convergent method.......................................................................................................... ........89 3-3 Reaction of polymer chains with a difunctional monomer......................................................89 3-4 Synthesis of a coupling agent with 18 chlorosilane functions.................................................89 3-6 Anionic synthesis of 4-arm st ar branched polystyrene using 1,2bis(dichloromethylsilyl)ethane as functionalizing agent.........................................................90 3-7 Halogen-lithium exchange reaction.........................................................................................9 0 3-8 Synthesis of 4-arm star branched polym ers using tetrabromome thylbenzene as linking agent.......................................................................................................................... ...............90 3-9 Synthesis of PI star polymer usi ng HFPO as multifunctional coupling agent........................90 3-10 Use of 1,3,5-tris(1-phenyletheny l)benzene as coupling agent..............................................91 3-11 Use of fullerene C60 as linking agent for star polymer synthesis...........................................91 3-12 Divergent method.......................................................................................................... ........91 3-13 Synthesis of three-armed poly(propylene sulfide) star..........................................................92 3-14 Synthesis of four-arm PS star by the In-Out method.........................................................92

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15 3-15 Application of the In-In method for star synthesis............................................................93 3-16 Synthesis of dilithiated ( 1 ), trilithiated ( 2 ), and tetralithiated ( 3 ) initiators.......................93 3-17 Scheme of the tetracarbanionic initiator/lithium 2-methoxyethoxide complex.............94 3-18 Synthesis of four-armed polystyrene stars.............................................................................94 3-19 SEC eluograms of (PS)4 polystyrene and (PB)4 polybutadiene stars....................................95 3-20 1H NMR spectra (CD2Cl2 ; 400MHz) of (PB-OH)4 and (PB-OH)3 hydroxyl terminated star polymers.................................................................................................................. .......96 3-21 Reaction scheme for the synthesis of SBM star block terpolymers.....................................97 3-22 SEC eluograms monitoring the formation of a P(Sb -Bb -M)2 pentablock copolymer........97 3-23 SEC eluograms monitoring the formation of a P(Sb -Bb -M)n (n = 3 or 4) star block terpolymer..................................................................................................................... ........98 3-24 1H NMR spectrum (CDCl3, 400 MHz) of P(Sb -Bb -M)3 star block terpolymer................99 3-25 Synthesis of (PBb -PEO)4 star block copolymers...............................................................100 3-26 1H NMR spectra (CDCl3 ; 400MHz) of a star copolymer (PB76b -PEO444)4......................101 3-27 SEC traces of the (PB-OH)4 precursor and of th e star copolymers (PB76b -PEOn)4 in THF............................................................................................................................ .........101 3-28 1H NMR spectra (200MHz) of (PB76b -PEO444)4 in CD2Cl2 (A) and in CD3OD (B).........102 4-1 Direct visualization of the 1% unreacted ( A ) and 0.05% cross-linked ( B ) wormlike micelles of PB45b -PEO55 diblock copolymer by cryotransmission electron microscopy....134 4-2 Formation and osmotic deflation of PB46b -PEO26 diblock copolymer, vesicles either without (A, B) or with (C) cross-lin king between the hydrophobic segments of butadiene...................................................................................................................... ..........134 4-3 Representation of the concept of a two-dime nsional network of molecular pores, i.e., perforated monolayers........................................................................................................ 135 4-4 A quasilinear coupler (a, p -xylylene dibromide), a cross-shaped monomer (b, lanthanum sandwich complex of tetrapyridylporphyrin), an idealized structur e (c), and an STM image (d) of a square grid..................................................................................................... .135 4-5 Amphiphilic porphyrins P1 and P2. P1: R = R1 (M = H2, Cu); P2: R = R2 (M = H2, Cu, Fe). Amphiphilic porphyrazine P3 (M = Cu).........................................................................136 4-6 General reactions involved in th e polymerization of alkoxysilanes......................................136

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16 4-7 Molecular structure of the lipopolymer polymerized by exposure to UV light....................137 4-8 Surface Pressure-Area per poly mer molecule isotherms at 298K for (PB76b -PEOn)4 star block copolymers (n = 57, 137, 444 and 1725).....................................................................137 4-9 Isotherm of (PB76b -PEO444)4 depicting how measurements of molecular area for the three principal regions are obtained.....................................................................................138 4-10 Linear dependence of Ap on the total number of ethylene oxide units................................138 4-11 Linear dependence of Apseudoplateau on the total number of ethylene oxide units...............139 4-12 Compression/expansion curves for two different samples of PB4b -PEO4 star block copolymers ((PB76b -PEO57)4 and (PB76b -PEO57)4) at (A) 5 mN.m-1, (B) 10mN.m-1 and (C) 15mN.m-1...............................................................................................................140 4-13 Evolution of transfer ratio with the surface pressure in the case of (PB76b -PEO1725)4 star block copolymer sample..............................................................................................141 4-14 AFM tapping mode amplitude images of the (PB76b -PEO1725)4 (A, B, C, D, E, F, G and H) and (PB76b -PEO57)4 (I and J) star block copolymer s transferred to a mica plate support at various surface pressures...................................................................................142 4-15 Dependence of the number of molecules per domain on the surface pressure in the case of the (PB76b -PEO1725)4 star block copolymer sample. Th e general trend shows that as pressure increases, more molecules aggregate (dramatic increase from = 4 mN/m) to form the observed circular PB microdomains....................................................................143 4-16 Model proposed to explain the formati on of a network of elongated stripes......................144 4-17 Surface Pressure-Area per polymer molecule isotherms for (PB200b -PEOn)3 star block copolymers (n = 76, 326, 970, and 2182)...........................................................................145 4-18 Linear dependence of Apseudoplateau on the total number of ethylene oxide units...............145 4-19 Surface Pressure-Area isotherms for (PB200b -PEO76)3 star block copolymer before and after cross-linking in the presence of AIBN under UV light ( = 20 mN/m).....................146 4-20 IR spectra of (PB200b -PEO76)3 before and after cross-linki ng in the presence of AIBN under UV light................................................................................................................. ...146 4-21 AFM topographic images of the (PB200b -PEO76)3 star block copolymer transferred to mica substrates ( = 20 mN/m) before (A) and after cr oss-linking (B, C, D, and E) at different reaction times....................................................................................................... 147 4-22 Hydrosilylation of the pendant d ouble bonds of the PB homopolymer..............................148 4-23 1H NMR spectrum (CDCl3 ; 300MHz) of the commercial linear polybutadiene................148

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17 4-24 1H NMR spectrum (CDCl3 ; 300MHz) of the hydrosilylated polybutadiene......................149 4-25 IR spectra of the polybutadiene before a nd after hydrosilylation.......................................149 4-26 Cross-linking reaction invol ving hydrolysis and condensa tion of the triethoxysilane groups of the polybutadiene backbone...............................................................................150 4-27 Surface pressure-Mean Molecular Area isot herms of the hydrosilylated polybutadiene carried out after different reac tion times (subphase pH = 3.0)...........................................150 4-28 Static elastic modulus-surface pressure curves of the hydrosilylated polybutadiene at different reaction times (subphase pH = 3.0)......................................................................151 4-29 Mean Molecular Area-Time isobars of the hydrosilylated polybut adiene for various subphase pH values ( = 10 mN/m)...................................................................................151 4-30 Removal of the cross-linked homopolymer from the Langmuir trough surface.................152 4-31 AFM topographic images of the LB film s transferred onto mica substrates at = 10 mN/m: the commercial polybutadiene (A) a nd the hydrosilylated polybutadiene at pH = 7.0 (B; t = 0 h) and 3.0 for different reacti on times (C ; t = 20 min and D; t = 10 h). (E and F) Cross-section analys is of the images C and D....................................................152 4-32 Hydrosilylation of the pe ndant double bonds of the (PBb -PEO)3 star block copolymer...153 4-33 1H NMR spectra (CDCl3 ; 300MHz) of (PB200b -PEO326)3 star copolymer and the corresponding hydrosilylated (PB78co -PB(Si(OEt)3)122b -PEO326)3 star block copolymer...................................................................................................................... .....154 4-34 IR spectra of the (PB200b -PEO326)3 star block copolymer and the corresponding hydrosilylated (PB78co -PB(Si(OEt)3)122b -PEO326)3 star block copolymer......................155 4-35 Surface Pressure-Area isotherms for (PB200b -PEO326)3 star block copolymer and the corresponding hydrosily lated (PB(Si(OEt)3)b -PEO)3 star block copolymer before (pH = 3.0, t = 0h) and after (pH = 3.0, t = 10h) cross-linking...................................................155 4-36 Surface pressure-Area isotherms (A) and Compressibility-Area curves (B) for the hydrosilylated (PB(Si(OEt)3)b -PEO)3 star block copolymer ca rried out at different reaction times (subphase pH = 3.0)....................................................................................156 4-37 Isobars of the hydrosilylated (PB(Si(OEt)3)b -PEO)3 star block copolymer for various subphase pH values ( = 5 mN/m).....................................................................................157 4-38 Removal of the cross-linked (PB(Si(OEt)3)b -PEO)3 star copolymer from the Langmuir trough surface. The dark yellow material easily comes off the subphase using a spatula........................................................................................................................ .........157

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18 4-39 AFM topographic images of the (PB(Si(OEt)3)b -PEO)3 star block copolymer LB films transferred to mica substrates at subphase pH = 7.0 (A; t = 0 h) and 3.0 for different surface pressures (B, C, D, E, F, G and H; t = 10 h)..........................................................158 4-40 AFM section analysis of the images of the (PB(Si(OEt)3)b -PEO)3 star block copolymer LB films transferred to mica s ubstrates at subphase pH 3.0 for different surface pressures (t = 10 h).................................................................................................15 9 4-41 AFM topographic images of the (PB(Si(OEt)3)b -PEO)3 star block copolymer LB films transferred to mica substrates at s ubphase pH = 3.0 (t = 10 h) before ( = 9 mN/m) and after ( = 2 mN/m) expansion of the monolayer................................................................159 4-42 Surface Pressure-Area isotherms for the hydrosilylated (PB(Si(OEt)3)b -PEO)3 star block copolymer cross-linked at subphase pH 3.0 (t = 10 hrs) for two different surface pressures ( = 5 and 20 mN/m)..........................................................................................160 5-1 Representative structures of asymme tric and miktoarm star polymers.............................190 5-2 Synthesis of three-arm asymmetric PS st ar using chlorosilane as linking agent...................191 5-3 Synthesis of (PS)2b -P2VP miktoarm star copolyme r by combination of linking and hydrosilylation reactions...................................................................................................... ..191 5-4 Synthesis of asymmetric PS star us ing DDPE derivative as coupling agent.........................191 5-5 Use of DPE derivative as branching agent............................................................................192 5-6 Representation of different tree -like macromolecular structures..........................................193 5-7 Representation of dendrimer growth by the divergent and convergent methods..................194 5-8 Synthetic route developped by Vgtle for the synthesis of branched polyamides................194 5-9 Synthetic route for the preparation of PAMAM dendrimers by the divergent method.........195 5-10 Synthesis of poly(et her amide) dendrimers.........................................................................196 5-11 Synthesis of poly(benzyl ether) dendrimers by the convergent method.............................197 5-12 Synthetic strategy toward dendrimer-like PEO...................................................................198 5-13 Synthesis of dendrimer-like copolymers PS3b -PEO6.........................................................199 5-14 Synthesis of a second-genera tion dendrimer-like PS by ATRP..........................................200 5-15 Synthesis of a third-generati on dendrimer-like poly(L-lactide)..........................................201 5-16 Functionalization of PMMA star chain ends by a TERMINI compound............................202

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19 5-17 Divergent iterative synthetic strategy elaborated for synthe sis of dendritic PMMA by a combination of LRP and TERMINI...................................................................................203 5-18 Synthesis of a secondgeneration dendritic P(S2I3) copolymer...........................................204 5-19 General reaction scheme for the synthe sis of third-generation dendritic PB.....................204 5-20 Synthesis of second-generation dendrime r-like PS by coupling reaction of living chains on chlorosilane star chain ends...........................................................................................205 5-21 Synthesis of second-generation dendrimer-like star-branched PMMA..............................206 5-22 SEC trace (RI detector) of polystyryllithi um living chains after reaction with 4,4dibromodiphenylethylene...................................................................................................206 5-23 Synthesis of asymmetric and miktoarm star (co)polymers..............................................207 5-24 SEC traces (RI detector) of PS(Br)2 aryl bromide-terminated polystyrene and its precursor PS-OH hydroxyl-terminated polystyrene...........................................................208 5-25 1H NMR spectra (CD2Cl2; 400 MHz) of PEO(Br)2 aryl bromide-terminated poly(ethylene oxide) and its precursor PE O-OH hydroxyl-termina ted poly(ethylene oxide)......................................................................................................................... .........209 5-26 1H NMR spectra (CD2Cl2; 400 MHz) of PB(Br)2 aryl bromide-terminated polybutadiene and its precursor PB -OH hydroxyl-terminated polybutadiene....................210 5-27 SEC traces (RI detector) of asymmetric star polystyrenes PSb -PS2 and its precursor PS-(Br)2............................................................................................................................... 211 5-28 SEC traces (RI detector) of asymmetric star polymer PBb -PB2 and miktoarm star copolymer PBb -PS2 and its precursor PB-(Br)2................................................................211 5-29 SEC traces (RI detector) of miktoarm star copolymers PSb -PB2, PSb -PI2, and its precursor PS-(Br)2...............................................................................................................212 5-30 1H NMR spectrum (CD2Cl2; 400 MHz) of an asymmetr ic star polybutadiene PBb PB2(OH)2.............................................................................................................................21 3 5-31 Synthesis of third-generati on dendrimer-like polystyrene..................................................214 5-32 SEC traces (RI detector) of PS4(Br)8 and PB4(Br)8 aryl bromide-terminated polystyrene and polybutadiene stars a nd its precursors (PS-OH)4 and (PB-OH)4 hydroxylterminated polystyrene and polybutadiene stars and the tetrabromoinitiator.....................215 5-33 1H NMR spectrum (CD2Cl2; 400 MHz) of (PB-OH)4 hydroxyl-terminated polybutadiene star............................................................................................................. ..216

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20 5-34 1H NMR spectra (CD2Cl2; 400 MHz) of PB4(Br)8 aryl bromide-terminated polybutadiene star............................................................................................................. ..216 5-35 SEC traces (RI detector) of dendrimer-like polystyrenes....................................................217 5-36 SEC/HT traces (RI detecto r) of (A) dendrimer-like polyst yrenes and (B) dendrimer-like polybutadienes................................................................................................................. ...218 5-37 1H NMR spectrum (CD2Cl2; 400 MHz) of a hydroxyl-terminated dendrimer-like polybutadiene PB4b -PB8(OH)8..........................................................................................219 5-38 1H NMR spectrum (CD2Cl2; 400 MHz) of a aryl bromid e-terminated dendrimer-like polybutadiene PB4b -PB8(Br)16..........................................................................................220 5-39 Evolution of the hydrodynamic radius (RH) as a function of the number of generation (G) for dendrimer-like polystyrenes prepared using tetrafunctional..................................221 5-40 Evolution of Log[] as a function of the number of generation (G) for dendrimer-like polystyrenes prepared using tetrafunctional.......................................................................221 5-41 Evolution of Log[ ] as a function of Log Mn for dendrimer-like polystyrenes prepared from tetrafunctional........................................................................................................... .222 6-1 Conceivable tetraca rbanionic initiator...................................................................................22 8 6-2. Synthetic strategy proposed fo r brush polymer preparation.................................................228 7-1 Synthesis of 1-pentadecyl-3-phenoxy benzene.....................................................................255 7-2 Synthesis of 1,3,5-tris(4-bromophenyl)benzene....................................................................255 7-3 Synthesis of 1,3-bis(p-bromophenyl)-2-propane...................................................................255 7-4 Synthesis of 2,3,4,5-tetrakis(p-b romophenyl)-cyclopentadienone........................................255 7-5 Synthesis of (1,2,3,4-tetrab romophenyl)-5-phenyl)benzene.................................................256

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21 Abstract of Dissertation Pres ented to the Graduate School of the University of Florida and the University of Bordeaux 1 in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy APPLICATION OF LITHIUM/HALIDE EXCHANGE REACTIONS TO THE SYNTHESIS OF COMPLEX POLYMER ARCHITECTURES: INVESTIGATION OF THEIR SELF-ASSEMBLING PROPERTIES AT THE AIR/WATER INTERFACE By Rachid Matmour August 2007 Chair: Randolph S. Duran Major: Chemistry An entire set of hydrocarbon-soluble polycarba nionic initiators and macroinitiators was synthesized by using a simple halogen-lithium ex change reaction (Gilmans reaction) carried out on multibromo molecule and macromolecule precursors. Using these multicarbanionic (macro)initiators an entire set of complex polym er architectures has been synthesized by anionic polymerization using a divergent method. This strategy was first applied to the preparation of simple polymer architectures such as poly(styreneb-butadieneb-styrene) triblock copolymers with excellent mechanical properties, obtained using a new hydrocarbon soluble dicarbanionic organolithium initiator containing a side C15-alkyl chain. The same exchange reaction has been succ essfully applied to generate triand tetracarbanionic species from trisand tetrakis-bromoaryl compounds. The use of a / ligand was instrumental in obtaining polycarbanionic initiators solubl e in apolar medium, and the subsequent preparation of various well-defined three and four-armed polystyrene and polybutadiene stars synthesized by the core-first method. The efficiency of the latter was even exploited to synthesize poly(butadiene-b-ethylene oxide) (PBb-PEO)n amphiphilic star block

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22 copolymers and poly(styreneb -butadieneb -methyl methacrylate) (P(Sb -Bb -M)n) star block terpolymers ( n = 3 or 4). The potential of PBb -PEO star block copolymer to self-assemble at the air/water interface was exploited to synthe size a two-dimensional polymeric nanomaterial consisting of a continuously cross-linked polybut adiene two-dimensional netw ork with poly(ethylene oxide) domains of controlled sizes trapped within the network. To reach that goal, novel (PB(Si(OEt)3)b -PEO)3 star block copolymers were designed by hydr osilylation of the pe ndant double bonds of (PBb -PEO)3 star block copolymer precursors with triethoxysilane. Self-condensation of the triethoxysilane groups under acidic conditions led to a successful cross-linking of the polybutadiene blocks directly at the air/water interface without any additives or reagents. Finally, the Gilman reaction was extended on -dibromo chain-end polymers after the introduction of a branching agen t whose halogen atoms are carried by separate aryl rings to afford hydrocarbon-soluble polycarbanionic macroini tiators. This provided an efficient synthetic route to the asymmetric and miktoarm star (c o)polymers based on the combination of different polymers such as polystyrene, polybutadiene, a nd polyisoprene. By the reiteration of this sequence of reactions (branching and halogen-lithium exchange reactions) starting from a tetrafunctional initiator, dendrimer-like PS and PB up to the seventh and third generations, respectively, could be successfully synthesized.

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23 Rsum du rapport de thse prs ent aux coles doctorales de lUniversit de Floride et de lUniversit Bordeaux 1 pour lobtention du grade de Docteur APPLICATION DE REACTIONS DECHANGE HALOGENE/LITHIUM A LA SYNTHESE DE POLYMERES A ARCHITECTURES COMPLEXES. ETUDE DE LAUTOASSEMBLAGE A LINTERFACE AIR/EAU par Rachid Matmour Dcembre 2006 Prsident de la commission dexamen: Randolph S. Duran Spcialit : Chimie des polymres Une nouvelle famille damorceurs et de macroamorceurs pluricarbanioniques solubles en solvant apolaire a t synthtise par une r action dchange halogne-lithium (raction de Gilman) effectue sur des composs halogns (m acro)molculaire. Lutilisation de ces espces pluricarbanioniques comme (macro)amorceurs a permis la synthse de diffrentes architectures polymres complexes par polymrisa tion anionique par voie divergente. Cette stratgie a tout dabord t applique la prparation darchitectures polymres simples telles que des copolym res triblocs poly(styrneb -butadineb -styrne), aux proprits mcaniques intressantes, obtenus laide dun amorceur dicarbanionique soluble en milieu apolaire et ce sans additif gr ce lajout dune chane alkyle de 15 carbones sur la structure de lamorceur. Cette mme raction dchange halogne-l ithium a t applique la prparation despces triet ttra carbanioniques partir de composs tr iet ttrabromoaryl. Dans ce cas, lutilisation de ligand / a nanmoins t ncessaire pour lobtention damorceurs multicarbanioniques solubles en milieu apolaire et la prparation de polystyrne et de polybutadine en toile trois et quatre branches synthtises pa r la mthode core-first

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24 Lefficacit de ces espces pluricarbanioniques a aussi t exploite pour la synthse de copolymres diblocs amphiphile s en toile poly(butadineb -oxyde dethylne) et de copolymres triblocs en toile poly(styrneb -butadineb -mthacrylate de mthyle) trois et quatre branches. Lintrt potentiel darchitectures polymres tels que les copolymres amphiphiles en toile poly(butadineb -oxyde dethylne) linterface air/eau a pu tre dmontr travers la synthse de nanomatriaux polymres bidimensi onnels bass sur un rseau en deux dimensions de polybutadine rticul possdant des domaines de poly(oxyde dethylne) de tailles contrles pigs au sein du rseau. Pour atteindre cet objectif, les blocs de pol ybutadine ont dabord t fonctionnaliss par des groupeme nts triethoxysilane aprs hydr osilylation des doubles liaisons pendantes du copolymre en toile poly(butadineb -oxyde dthylne). La condensation des groupements pendants triethoxysilane sous conditions acides a ainsi permis la rticulation des blocs polybutadine directement linterf ace air/eau.block copolymers and poly(styreneb butadieneb -methyl methacrylate) (P(Sb -Bb -M)n) star block terpolymers ( n = 3 or 4). Lutilisation de la raction de Gilman a fi nalement t tendue la prparation de macromamorceurs pluricarbanioniques solubles en milieu apolaire partir de chanes polymres possdant un groupement dibrom en extrmit de chane, aprs lintroduction dun agent de branchement dont les atomes dhalognes sont ports par deux noyaux aromatiques diffrents. Cette mthode a permis llabora tion de (co)polymres en toile asymtriques et miktoarms constitus de polystyrne et polydines. La rptition de cette squence de ractions (branchement et raction dchange halognelithium) en partant dun amorceur ttrafonctionnel a ainsi amen la synthse de dendrimres de polystyrne de septime gnration et de polybutadine de troisime gnration.

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25 CHAPTER 1 POLYLITHIATED SPECIES: APPLICATION TO POLYMER SYNTHESIS 1.1 Introduction For many years it was thought by organic chemists that it was impossible to prepare polylithium organic compounds de fined as organic compounds cont aining two or more lithium on the same or adjacent carbons. It was widely belie ved that having two lithiums on the same or adjacent carbon atoms would lead to a destabiliz ation and lithium hydride elimination. This misconception was changed in th e early 1970s by work of West1 and Lagow.2 Actually, there are four distinct methods to quantitatively conve rt a multifunctional compound to polylithiated species. 1.2 By Reaction with Lithium The reaction with lithium metal or vapor on di fferent categories of molecules such as alkanes, alkenes, aromatics, or also alkyl and aryl halide was the first synthetic method discovered for the preparation of polylithium organic compounds. The use of lithium metal, notably used for the synthesis of butyllithium, was first reported in the early 1950s by West et al.1,3,4 with the conversion of 1,5-dichloropentan e to 1,5-dilithio compound. This strategy was later developed by the Lagow group5-13 with the reaction at high te mperature of lithium vapor with halogenated organic compounds as a ge neral synthesis for pol ylithium compounds. However, extremely low yield reactions with a mixture of compounds avoid any purification or characterization of the pure product. This very low yield is explained first by lithium-halide elimination occuri ng from molecules having a halide and a lithium on the same or adjacent carbons producing carbenes and lithium ha lides. Furthermore, the reaction of lithium on the halide compound is in competition with a secondary reaction of intermolecular coupling reaction between the lithiated species and the alkyl halide reagent (Wurtz coupling)14 (Figure 1-

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26 1) which has no serious consequence for a monof unctional initiator, but not for the case of pluricarbanionic compounds. 1.3 By Reaction of Alkyllithium on Mu ltifunctional Unsaturated Molecules The most recent method is based on the reacti on of alkyllithium on th e unsaturations of a multifunctional agent. This strategy was first app lied for the synthesis of dilithiated compounds by reaction of butyllithium on dif unctional unsaturated reagents such as divinylbenzene (DVB) derivatives,15,16 or double diphenylethylene (DDPE) derivatives.17-19 The latter dilithiated species were actually used, as shown below (Chapter 2), for the preparation of poly(styreneb -butadieneb -styrene) (SBS) triblock copolymers. By using this strategy, only one group was successful in the preparation of pluricarbani onic species of functi onality higher than 2. Indeed, Quirk and Tsai20 synthesized tricarbanionic species, soluble in apolar solvents by re action of 3 moles of sec -butyllithium with 1,3,5tris(1-phenylethenyl)benzene (tri-D PE) as presented in Figure 1-2. This hydrocarbon-soluble in itiator was found to be efficient for the anionic polymerization of styrene, but only when THF was also added in the reaction mixture ([THF]/[Li] = 20). The addition of THF as a polar additi ve modified the aggregation rate of the pluricarbanionic species and gave by the same way a quantitative initiation. The same initiator was also used to produce three-arm polybutadiene stars.21 Even though a complete monomer comsumption was observe d, the size exclusion chromatography (SEC) analysis showed a bimodal distribution. This beha vior was attributed to the strong aggregation effects of the trifunctional in itiator in a non polar solvent. The problem was overcome when s BuOLi was added in the reaction mixture in a ratio [ s -BuOLi]/[Li] = 2. s -BuOLi was shown to be capable of disrupting the initiator association without affecting apprecia bly the microstructure of the polybutadiene chains.

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27 The limitations of the method include the extr eme care that should be exercised over the stoichiometry of the reaction between s -BuLi and tri-DPE to avoid the presence of a second population of linear polymers or the formation of initiators of lower functionality and the fact that a minimum arm mol ecular weight of around 6.103 g.mol-1 is required for the growth of the polymer chains on the three carban ionic sites at the same time. By the same manner, the Mller group22 employed polylithiated carbosilane dendrimers, as multifunctional initiator (Figure 1-3). The dendrimers had 16 or 32 allyl groups at their periphery. A hydrosilylation route was performed to react ha lf of these terminal allyl groups with didecylmethylsilane (Figure 1-3). The remaining allyl groups were lithia ted by the addition of s BuLi, to produce the multifunctional initiators. Thes e initiators carrying theoretically 8 or 16 carbionic sites were soluble in polar solven ts (THF) and were subsquently used for the polymerization of styrene, ethylene oxide, and hexa methylcyclotrisiloxane (D3). The polymer stars obtained demonstrated a monomodal molecu lar weight distribution. However, molecular weight characterization data were not provided in this study and the nu mber of branches for these stars was not determined, thus leaving unce rtain the formation of the desired structures. Parallel to these pluricarbanionic species of precise functionality, many research groups worked on the synthesis of multifunctional initi ators most certainly less well-defined, but allowing the access to star polymers with a very high number of branches. First demonstrated by Eschwey et al.23,24 and later developped by Rempp and colleagues25,26 DVB was polymerized by butyllithium or naphtalene lithium in benzene at high dilution to obta in a stable microgel suspension. These heterogeneous microgel nodules, which were de scribed as living microgel nodules covered by living anionic sites (for example, by using a ratio of [DVB]/[BuLi]=2, a microgel with a molecular weight of Mn = 1.9 x 103 g.mol-1 and a polydispersity of 16.8 could be

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28 obtained)24 (Figure 1-4), were subsquently used as multifunctional initiators to polymerize styrene, isoprene, or butadiene. However, it should be noted a relatively bad control over the star functionality since it is impossi ble to predict the number of branches using this method. A slight variation was adopted by Okay and Funke27,28 The polymerization of DVB was initiated by living poly( tert -butylstyryl)lithium chains having low molecular weights in order to avoid the solubility problems arising from the strong association of th e carbon-lithium functions in the nonpolar solvent. By using this strategy, Rempp and colleagues26 synthesized poly( tert butyl acrylate) (P t BuA) and poly(ethylene oxide) (PEO) star s. The synthesis was performed in THF to minimize the strong association effects, using naphtalene lithium or cumyl potassium to polymerize DVB for the P t BuA or PEO star synthesis, re spectively. DVB polymerization was initiated by electron-transf er instead of by additi on. The polymerization of t BuA was carried out at C in the presence of Li Cl after the active centers have been reacted with a suitable amount of 1,1-diphenylethylene (DPE) to reduce th eir nucleophilicity. It was found that the mole ratio [DVB]/[Li+] should vary between 1.5 and 2.5 to afford a stable microgel suspension. The molecular characteristics of the final products and the calculated molecular weight of the branches determined by SEC and light scattering (LS) revealed the existence of multimodal molecular weight distribution with large numbe rs of arms, ranging from 22 to 1300 and from 5 to 219 for the P t BuA or PEO stars, respectively. 1.4 By Lithium-Halogen Exchange Reaction The third method based on the exchange reac tion between a halide and a metal described by Gilman et al.29 is one of the most used methods for th e preparation of aryl lithium species. It consists in the reaction of an aryl halide, such as bromobenzene, with an alkyllithium, typically butyllithium (Figure 1-5).29,30 This equilibrated reaction is str ongly displaced to the most stable lithiated compound and was described as quanti tative under certain conditions. The Wurtz

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29 coupling reaction (Figure 1-1), non negligible in the cas e of alkyl bromides, does not happen in the case of aryl bromides due to the low nucleophilicity of phenyllithium toward the bromide compounds.14 Thus, Lagow and colleagues31,32 used this halogen-lithium exchange reaction notably for the synthesis of hexalithiobenzene from the hex achlorobenzene, but with a relatively low yield (53%). By the same manner, some other groups took advantage of this halogen-lithium exchange reaction for molecule functionalization. Kleij et al.33 developed a useful synthetic procedure for the incorporation of the potential ly multidentate monoanionic ligands via the para-position on the periphery of carbosilane dendrimers. Dendritic carbosilanes functionalized with (N)CNPh-Br end groups could be selectivel y lithiated in presence of t -BuLi in Et2O to give their multilithiated aminoaryl derivatives with stable C-Li bonds whic h were used to introdu ce various metals such as Pt via lithiation/tran smetalation sequences. Jayaraman and Nithyanandhan34 proposed also another example of dendrimer functionalization through an effi cient halogen-lithium exchange reaction. Poly(alkyl aryl ether) dendrimers were functionalized w ith bromophenyl groups at their pe riphery so as to have 3, 6, 12, and 24 groups in the zero, first, second, and third generation dendrimers, respectively. The bromophenyl functionalized dendrimers were conve rted quantitatively to their polylithiated derivatives by reaction with n -BuLi in benzene. Although the polylithiated dendrimers precipitated as a white solid, they were reacted either with D2O or with CO2, so as to afford the corresponding deuterated and carboxylic acid functionalized dendrimers, respectively. The carboxylic acid functionalized dendrimers were modi fied further to methyl esters during their characterization.

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30 The Sa group35 proposed the generation of polylithi ated derivatives of salicylic and oligosalicylic acids soluble in THF by means of the halogenmetal exchange reaction from bromo-substituted salicylic and oligosalicylic ac ids, including some with base-sensitive chiral centers avoiding the need to use protecting groups. These polylithiated species were notably used for the introduction of specifi c functions (-SMe, -CH(OH)C6H5, or C(=O)OEt) under these conditions. More recently, a two-step synthetic procedur e towards coil-rod-coil triblock copolymers was developed by Tsitsilianis et al.36 In the first step, -oligophenylenes (rod part) were modified by halogen-lithium exchange reaction to anionic bifunctional ini tiators soluble in THF (Figure 1-6). In the second step, flexible chains were grown from both ends of the rod part by an anionic polymerization procedur e leading to polystyrene-rod-pol ystyrene and/or poly(2-vinyl pyridine)-rod-poly(2-vinyl pyridine) triblock copolymers. It should be noticed that the yield of th e halogen-lithium exchange reaction depends on different experimental parameters such as the concentration in bromide compound, the nature of the solvent, the temperature and the na ture of the alkyllithium agent used.37-41 Although n -BuLi was the most used until now, Tsitsilianis et al.36 demonstrated that the reaction is quantitative in presence of s -BuLi for the aryl bromide compounds. t -BuLi is rather used for the iode/lithium exchange reaction.42 The concentration of the bromo precursor [Ar-Br] = 5.3.10-2 mol.L-1 was found by Trepka and Sonnenfeld40 to be the most appropria te for a good conversion to phenyllithium species (> 95%). The exchange reaction could be done either in apolar40 or polar solvents,29 the most appropriate being the one in wh ich the polylithiated compound is soluble. However, in the case of polar solvents th e reaction should be done between and C because of the low stability of the lithiated spec ies in polar solvents such as THF or dimethyl

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31 ether. Indeed, lithiated compounds could react with ether functions to form by cleavage reaction alkene and lithium alkoxide.14 In the case of apolar solvents su ch as cyclohexane or benzene, the reaction could be done at room temperature w ith no limitation in term of temperature. 1.5 By Reaction with a Base The last method was less used with only a few cases proposed. This method consists in removing an acidic proton by metalation or with the help of a base. For example, Fujimoto et al.43 were successful in preparing a soluble pl uricarbanionic initiator in a mixture of THF/diglyme by reaction of 1,3,5-tris-( -methoxybenzyl)benzene and a mixture of sodium/potassium. However, this trifunctional initiat or was not able to quantitatively initiate the polymerization of -methylstyrene leading to a mixture of linear chains, dimer species, and star polymers. Hogen-Esch and colleagues44 also proposed the synthesis of a trifunctiona l initiator by metalation of 1,3,5-tris[2-(2-pyri dyl)ethyl]benzene in presence of -dipotassiomethylstyrene. Used as initiator for the polymer ization of 2-vinylpyridine and 4-vinylpyridine in THF, the latter compound leads to polymer sample s with large molecular weight distribution and residual initiator. Studies of the reaction of ba ses on trimethylbenzene have shown the formation of a mixture of mono-, di-, a nd trilithiated species under these conditions. Although the use of a Lochmann base by Gordon et al.45,46 allowed the formation of pure tricarbanionic species by trimetalation of 1,3-cycloheptadiene in pentane, no interest was found in this polylithiated species as initiator fo r the polymerization. 1.6 Conclusion The reasons that are generally held respons ible for polylithiation to be impractical especially when the halogens to be substituted happened to be on the same carbon or on adjacent carbonsare two-fold. -Lithium-halide eliminations and in termolecular couplings between the

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32 lithiated reagent and the halide-substituted species are two important competing reactions that have long prevented polylithiation reactions from being practically considered. Another reason for the little attention given to multiple meta l-halide exchanges is because polylithiated compounds exhibit limited solub ility in most organic solven ts, forming rather insoluble aggregates of little utility. Added to the previo us complications, different requirements have to be fulfilled by a multifunctional initiator in order to produce polymers with uniform arms, low molecular weight distribution, and controllable mol ecular weights. All the initiation sites must be equally reactive and have the same rate of init iation. Furthermore, the initiation rate must be higher than the propagation rate. For instance, in polymer chemistry polylithi ation has never been contemplated for the reasons mentioned above; had it been mastered and the experimental conditions worked out polylithiation would be a viable and straightforwar d route to prepare multicarbanionic initiators for the subsequent synthesis of star-shaped polym ers. So far the only po ssibility of generating such multicarbanionic initiators was lithiation by addition to multivinyl compounds, but the very small number of reports on this strategy of synthe sis indicates that it is not that convenient a route. It indeed requires the prior synthe sis of multivinyl compounds that would not homopolymerize upon addition of organolithium r eagents. These constraints explain why the only initiator of precise functiona lity (higher than 2) ever synthesized by this method is the tricarbanionic compound of Quirk and Tsai20 who obtained it upon addition of sec -butyllithium onto a molecule containing three 1,1-diphenyle thylene-type unsatura tions (Figure 1-2).

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33 Figure 1-1. Wurtz coupling reaction. Figure 1-2. Synthesis of a tricarbanionic initiator. Figure 1-3. Synthesis of polylit hiated carbosilane dendrimers. R-Li +R'-X R-R'+LiXX : Halide atom R and R' : Alkyl groups s -Bu s -Bu s -Bu Li Li Li 3 sec-BuLi BenzeneSi Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si s-Bu s-Bu s-Bu s-Bu s-Bu s-Bu s-Bu s-Bu Li Li Li Li Li Li Li Li 8 sec -BuLi THFSi Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si s-Bu s-Bu s-Bu s-Bu s-Bu s-Bu s-Bu s-Bu Li Li Li Li Li Li Li Li 8 sec -BuLi THF

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34 Figure 1-4. Synthesis of pluri carbanionic species from DVB. Figure 1-5. Halogen-lithiu m exchange reaction. Figure 1-6. Synthesis of a dicarbanionic initiator from a dibromo precursor. Li Li Li Li Li Li Li Li s-BuLi + Br +RLi Li + R-Br Br Br 2 s -BuLi Li Li THF

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35 CHAPTER 2 A NOVEL ADDITIVE-FREE DICARBANIONIC INITIATOR FOR THE SYNTHESIS OF POLY(STYRENEb -DIENEb -STYRENE) TRIBLOCK COPOLYMERS IN NON-POLAR MEDIUM 2.1 Introduction Living anionic polymerization is certainly the most reliable and versatile technique for the synthesis of block copolymers.47,48 Under appropriate conditi ons anionic polymerization indeed proceeds in absence of transfer and termination reactions for a large number of monomers. For this reason, it occupies a ke y position in the industrial production of block copolymers, the most emblematic being SB S triblock copolymers comprising a low Tg polybutadiene block flanked by two glassy pol ystyrene end blocks. Such triblocks are industrially obtained by sequent ial polymerization of styren e and butadiene initiated by butyllithium (BuLi), followed by the deactivatio n of growing living carbanionic chains by a difunctional elect rophilic reagent.49-51 Although applied for the last forty years this method is very sensitive to the stoichiometry of the fina l dichain coupling, and ther efore fails to deliver diblock-free pure triblock copol ymers. The presence of diblock contaminants in the final sample is detrimental to excel lent stress-strain properties% decrease in tensile strength due just 5% of diblocksand prejudicial to its ultimate in commercial applications.52 The use of a dicarbanionic initiator that could trigger polymerization in two directions and afford SBS triblocks by a two-step sequent ial monomer addition therefore a ppeared as the only viable alternative.15,53 However, one major difficulty met in the latter case is the limited solubility of dicarbanionic initiators in apolar solvents, me dia that are required for the preparation of a polybutadiene (PB) central block with a high c ontent in 1,4-PB units and elastomers with optimal properties (high tens ile strength and elongation at break). Although a number of patents and papers have reported on the synthe sis of various organolithium diinitiators in nonpolar solvents, none of them coul d be practically used to prep are well-defined SBS triblock copolymers with a large content in 1,4 linka ges and equal amounts of cisand trans-

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36 unsaturations. Whether obtained by reaction of BuLi with appropriate diol efinic species in 2:1 ratio (m-diisopropenylbenzene,16,54-72 double diphenylethylene-type molecules17,18,73-82 or more complicated precursors19,83,84) or by generation of ion-radi cal species which then couple (electron-transfer from lithium to -substituted vinyl monomers),52,85-103 all these organolithium diinitiators indeed require the presence of ac tive polar additivesoften in small proportionsto efficiently in itiate polymerization, modifyi ng the stereochemistry of the polydiene block and increasing its content in 1,2 unsaturations. A dicarbanionic initiator that would be entirely soluble in apolar medium in absence of any additives or ligands and yet reactive enough is thus still in great demand. 2.2 Literature Overview on Symmetr ic ABA Triblock Copolymers Linear triblock copolymers consisting of tw o chemically different monomers of the symmetric type contain three bl ocks of A and B monomers arra nged in a way that the first and the third block have the same chemical na ture and molecular weight, whereas the middle block differs in chemical nature. There are th ree possible procedures to synthesize block copolymers of this type. 2.2.1 Sequential Monomer Addition The preparation of block copolymers by seque ntial addition of mono mers using living anionic polymerization and a mono functional initiator is the most direct method for preparing well-defined block copolymers. In this reactio n scheme (Figure 2-1), the first monomer is polymerized by an alkyllithium initiator follo wed by the polymerization of the second one. After complete consumption of the second monome r, an equal amount of the first monomer is added to the reaction mixture resulting in an ABA triblock copolymer (Figure 2-1). This approach involves three monomer add itions, and, therefore, the probability of partial termination of growing chains during the second or the third reaction step increases, due to impurities present in the monomers used. This can result in the presence of undesirable

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37 homopolymer A and/or diblock AB in the final product. Furthermore, small differences in the quantity of monomer A used in the first and third step may result in the synthesis of a triblock, which is not perfectly symmetric. Anothe r point that must be c onsidered is the ability of monomer B to initiate polymerization of mono mer A. If this criterion is not fulfilled, illdefined products will be obtained. This critic al aspect can be illustrated by considering the preparation of SBS triblock copolymers. Ind eed, the rate of the crossover reaction of polybutadienyllithium to styrene monomer to form polystyryllithium chain end is slow compared to the rate of styrene propagati on (order of reaction rate constants is kSB>kSS>kBB>kBS).104 Because of the slow rate of styren e initiation relative to propagation, a broad molecular weight distribution would be expected for the final polystyrene block segments. To obtain polystyrene end blocks w ith narrow molecular we ight distributions, a Lewis base such as an ether or amine is ofte n added before styrene monomer addition in this third stage of the triblock copolymer synthesis.50,53,105-108 Sometimes even monomer A may not be able to initiate polymerization of mono mer B appropriately. A typical example is the preparation of PI-PS-PI triblock copolymers.109 Initiation of styrene by PILi can be successful if a small amount of THF is used before the addition of styrene,109 but one should have in mind that the presence of THF will alter the microstructure of the third PI block. It is obvious that the outlined method cannot be used in th e present example if high 1,4-microstructure of the PI blocks is desired. Howeve r, it can be applied in the cas e where the 1,4-microstructure is not essential. In this case THF can be adde d from the beginning of the polymerization and both end PI blocks will have the same microstructure. 2.2.2 Coupling of Living AB Chains Another general method for the of ABA tr iblock copolymers involves first the synthesis by a two-step sequential monome r addition sequence of a living AB diblock copolymer, having the same composition but half the molecular weight of the final triblock

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38 copolymer. Then an appropriate coupling ag ent, i.e. a compound having two functional groups able to react with the ac tive anions forming covalent bonds, is used to connect two AB chains producing the desired symmetric triblock copolymer (Figure 2-2).49-51 This two-step method with coupling offers many advantages over the three-step sequential monomer addition method. From a practical point of view the polymerization time is reduced to onehalf that required for the three-step synthesis of a triblock copolymer with the same molecular weight and composition.110 One problem avoided in the two-step process is that the final crossover step from polybutadienyllithium or po lyisoprenyllithium to styrene is eliminated. The elimination of the third monomer additi on step also decreases the possibility of termination by impurities in a third monomer a ddition. However, caution should be exercised in the stoichiometry of the coupling reaction. In practice, it is di fficult to control the stoichiometry of the coupling r eaction and many two-step synthese s yield triblock copolymers with significant amounts of uncoupled diblock contaminants.110-112 Indeed, excess of living anions is usually used to ensure complete r eaction of both groups of the coupling agent. In general, the presence of diblock material affects the triblock copolymer morphology,112 which has a detrimental effect on physical properties of triblock copolymers (ultimate tensile strength and elongation at break).107,110 This makes necessary an ad ditional fractionation step in order to separate the AB A triblock copolymers from ex cess AB diblock copolymers. Finally, the coupling reaction may be completed in days. Obviously, this synthetic route is more time consuming than th e sequential a ddition method. PS-PI (or PB)-PS triblock copolymers have been synthesized by the coupling method by Morton and co-workers (Scheme 2-2).53 A PS-PD diblock is formed first where the length of the polydiene (PI or PB) block is half of that in the fina l triblock copolymer. Then the living diblocks are coupled using (CH3)2SiCl2 as the coupling agent. A small excess of the living diblock is used in orde r to ensure complete coupling. Solvent/nonsolvent fractionation

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39 of the crude product is performe d in order to isolate the pur e triblock copolymers. These triblocks have found applications as thermoplastic elastomers in everyday life. PD-PS-PD symmetric triblock copolymers can also be made in the same way. (CH3)2SiCl2 can also be used as a coupling agent for PS (or PD)-polysiloxane living diblocks in order to produce triblocks with a siloxane central block.113,114 When the outer blocks are PB with high 1,4microstructure, PE-PDMS-PE triblocks with semicrystalline outer and elastomeric inner blocks are obtained by hydrogenation of the parent PB-P DMS-PB materials.114 Another advantage of the two-st ep process is that it is mo re versatile with respect to the chemical composition of the center block. W ith the two-step method, the center block can be a more reactive monomer that would not be capable of reinitia ting polymerization of styrene because of the increased stabili ty of the chain end (Figure 2-3). For example, bis(bromomethyl)benzene has be en used as a coupling agent in cases where living (meth)acrylate (M) and vinyl pyridine (2VP) anions were involved.115 Due to the greater reactivity of the C-Br bond, this agent is efficient for coupling less reactive anions at lower temperatures (Figure 2-3). Well-defined symmetric triblock c opolymers with pyridine or (meth)acrylate central blocks ca n be prepared in both cases. Varshney et al.116 used terephthaloyl chloride as the coupling agent for the synthesis of AB A symmetric triblock copolymers with PS, P2VP, or polydiene of high 1,4 microstructure end blocks, and poly( tert butyl acrylate) middle blocks. The P t BuA blocks could be converted to other types of acrylic blocks by transesterification reactions, lead ing to a larger variety of ABA triblock copolymers. 2.2.3 Use of a Difunctional Initiator One of the most versatile methods for the synthesis of symmetric ABA triblock copolymers is the use of a difunctional initiato r, i.e., an organometallic compound having two anionic sites able to initiat e polymerization, in a two-step sequential monomer addition

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40 sequence. The middle B block is formed first followed by the polymerization of A monomer. A number of difunctional initia tors soluble in polar and/or nonpolar solvents have been reported in the literature.15-19 The points that deserve attention are: I i) The quality of the difunctional initiato r used, which is essentially its ability to form pure difunctional polymer. This depends on the precise chemical structure of the initiator and sometimes the solv ent medium as well as the chem ical nature of the monomer used. Not all known difunctional initiators beha ve in the desired manner in all solvents commonly used for anionic polymerization an d towards any available monomer. If the initiator/solven t/monomer system cannot generate pure difunctional polymer s, it is obvious that the final product will be a mixture of homopolymer, diblock, and triblock copolymer. ii) The purity of the monomers must be high in order to avoid de activation of one or both initiators active sites or lead to premat ure termination of grow ing chains, which will result in a mixture containing the desired tr iblock and other undesired impurities that are difficult to be eliminated by fracti onation or other separation methods. In our case, we will be especially inte rested in the hydrocarbon-soluble dilithium initiators required for the twostep synthesis of polystyreneb -polybutadieneb -polystyrene triblock copolymers. Indeed, a hydrocarbon-s oluble dilithium initiator ensures that the polydiene center block will have a high 1,4-mi crostructure and a correspondingly low glass transition temperature. 2.2.3.1 Divinylbenzene derivatives Adduct of divinylbenzene (DVB) derivatives with s -BuLi were the first examples of difunctional initiators st udied since th e early 1970s.54,58,59 Different studies on DVB demonstrated first that the two unsaturations of the meta isomeric compound were equally reactive to BuLi, in opposition to the conjugat ed unsaturations of the para compound (1,4DVB). However, a mixture of soluble monoa nd dilithiated and oligom eric species, with

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41 functionality higher than two due to possible polymerizati on of DVB, was obtained which did not guarantee a good control of the diene polym erization. Another dilithium initiator claimed by Rempp and colleagues59,61 was a bis-adduct of BuLi onto m -Diisopropenylbenzene ( m DIB), which was an efficient bi functional initiator in apolar solvent that affords a good control over the molar mass and narrow molar ma ss distribution even in the presence of a mixture of multiadduct, diadduct and unreacted sec -BuLi. Foss et al.58 and Cameron et al.60 have also used m -DIB as a difunctional pr ecursor, but had to add a -complexing polar agent such as triethylamine (Et3N) to avoid precipitation of the initiator. However, even in the presence of Et3N a mixture of species was still ob served after the reaction between m -DIB and sec -BuLi. We have to wait the work of Yu et al. ,64-66 who also revisited these experiments and demonstrated that the use of precursors su ch as 1,3-diisopropenylbe nzene with twice the amount of sec -BuLi in non-polar medium such as cy clohexane did not result in a soluble well-defined truly bifunctional initiato r; they found that the reaction of tert -BuLiinstead of sec -BuLiand 1,3-DIB in the pres ence of 1 equivalent of Et3N at C can lead to a welldefined difunctional initiator, i.e. 1,3-bis( 1-lithio-1,3,3-trimethylbut yl)benzene (DiLi) (Figure 2-4). Some other -complexing polar agents such as diethyl ether, tert -butyl methyl ether, N,N,N,N-tetramethylethylenediamine (TMEDA) and THF were found to be efficient polar additives, but leading to a high 1,2 -microstructure of the PB block.68 The same group finally demonstrated that the combination of the in itiator seeding techni que and weakly polar additives such as tert -BuOLi and anisole was necessary to prevent the presence of residual initiator and achieve equal reactivity of both ends active centers so as to obtain SBS and MBM triblock copolymers with high content of 1,4-PB units.68 -Complexing agents such as 1,2,4,5-tetramethylbenzene (durene) or tetraphenylethylene (TPhE) were also proposed which

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42 did not interact so strongly as -complexing agents with the Li+ cation to bring about the dissociation of the organolithium aggregates.69,70,72 2.2.3.2 Diphenylethylene-type molecules Other researchers concentrated thei r efforts on the reaction of double Diphenylethylene-type (DDPE) molecule s with stoichiometric amount of sec -BuLi in nonpolar solvents. Broske et al.76,78 observed at 60C after 2 hours in cyclohexane in presence of a small excess of sec -BuLi the formation of a soluble well -defined difunctional initiator with a negligible quantity of oligomers. It was demonstrated that this difunctional initiator was efficient in the case of the butadiene polymer ization, but only at low monomer conversion. Later, Quirk and Ma79 reported that the dilithiu m initiator based on 1,3-di(1phenylethenyl)benzene (PEB), although soluble in hydrocarbon solvents such as cyclohexane and benzene, led to bimodal molar mass distribution for molar masses lower than 50,000 and 150,000 g.mol-1 in the cases of PS and PB, respectiv ely. This is only after the addition of sec butoxylithium ( sec -BuOLi) as an additive that PB samples were obtained with a narrow molar mass distribution and a high conten t of 1,4-PB units (Figure 2-5).79 More recently, Tung and Lo,17,18,80-82 who first proposed the idea of using DDPE as precursors, developed dilithium initiators ba sed on different derivati ves of DDPE (Figure 26), which were soluble in benzene, cyclohexane and/or toluene depending on the structure of the DDPE derivative. Although the addition re actions of these la tter precursors with sec -BuLi were found to be clean and rapid, the resulting dilithiu m initiators were in soluble forming fine suspensions, which would coagulate into hard particles after seve ral hours. The fine suspensions were effective in initiating butadiene or isoprene polymeriza tion, but only after solubilizing the dilithium initiators by using additives such as N,N,N,N,Npentamethyldiethylenetriamine (PMDETA) an d lithium alkoxides or by reaction with a

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43 fractional amount of diene first an d then with the rest of the monomer, also called seeding technique. Finally, more complicated precursors such as -bis(phenylvinylidenyl)alkanes19,83,84 and -bis(isopropenylphenyl)alkanes19,83,84 or some other listed below (Figure 2-6) were developed and found to be effective for the polymer ization of styrene or diene, but difficult to synthesize. 2.2.3.3 Use of alkali metals Another way of making diini tiators consists in the reaction of alkali metals with substituted vinyl monomers.88,89,91-101 For example, this reaction is useful for the preparation of homogeneous difunctional initiators from -methylstyrene in polar solvents such as THF. Because of the low ceiling temperature of -methylstyrene, dimers or tetramers can be formed depending on the alkali metal system, te mperature, and concen tration. SBS triblock copolymers were synthesized using a dicarbanion ic initiator formed by the reaction of lithium metal and -methylstyrene (Figure 2-7).89 However, the presence of THF needed for the formation of the dicarbanionic initiator resu lted in SBS triblock copolymers with poor mechanical properties. Many aromatic hydrocarbons such as naphtal ene can also react with alkali metals by reversible electron transfer in polar aprotic solv ents such as THF to form stable solutions of the corresponding radical anions (Figure 2-8).47,48,102,103 PEO-PI-PEO symmetric triblock copolymers were synthesized using sodium or potassium naphthalene as the difunctional initiator.103 Isoprene was polymerized first followed by addition of EO (Scheme 2-8). The copolymers had a variety of block compositions and total molecular weights. Their molecular weight distributions were narr ow and monomodal. Since Na or K naphthalenide is soluble only in polar solvents (e.g., THF), the microstr ucture of PI obtained was mostly 3,4. Thus, these initiators are of limited utility for the preparation of elastomeric block copolymers

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44 because they are prepared and ut ilized in polar solvents such as THF that result in polydiene with high vinyl microstructures and relatively high Tg values. 2.3 Results and Discussion We reported in chapter 3 the preparation of triand tetrafuncti onal polylithium organic compounds by lithium-halogen exchange and their use as initiators for the synthesis of polystyrene (PS) and polybutadiene star polymers and SBM triblock star copolymers (Chapter 3).121 This method rests on the meta llation of poly(arylh alide)s whose haloge ns are carried by separate aryl rings. However, the polylithiated sp ecies formed are soluble only in the presence of / -coordinating ligands. We propose here a new dicarbanionic initiator that is totally soluble in apolar media in absence of any add itive, and is efficient enough to generate welldefined telechelic PB and SBS triblock c opolymers with a high content in 1,4-PB units.122,123 For this purpose, 3-pentadecyl phenol, obtained from cashew nut shell,124,125a renewable resource material a nd by-product of agro industrys erved as a precursor for the dibromo compound viz, 1-bromo-4-(4-bromophenoxy)-2-pentadecyl benzene126 ( 1 ); the latter was subsequently dilithiated and eventually used for difunctiona l initiation. In this chemistry advantage is taken of the sa turated 15-carbon side chain to obtain a soluble dilithiated initiator. The dibromo compound 1 was synthesized by a two-step synthetic procedure (Figure 2-9). In the first step, 1-pentadecyl-3-phenoxy benzene was prepared by reaction of potassium 3-pentadecyl phenolate (product of the depr otonation of 3-pentad ecyl phenol) and bromobenzene. In the second step, the dibromoprecursor 1 was obtained in excellent yields (84 %) after bromination in para position of 1-pentadecyl-3-phenoxy benzene (Figure 2-9). The structure of the dibromo compound (1 ) was confirmed by 1H and 13C NMR spectroscopy and mass spectrometry (Figures 2-10 and 2-11).

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45 Next, 1 was treated with stoichiometric amounts of sec -butyllithium ( s -BuLi) in cyclohexane to generate 1 and 2-bromobutane (Figur e 2-12). Among the different alkyllithium reagents sec -butyllithium was found to be the most efficient for the bromide/lithium exchange reaction (quantitative reaction with no side reactions such as coupling and elimination).36 tert -Butylithium is more suitable for the iodine/lithium exchange reaction.42 To avoid any chance of deactivation of the growing carbanionic chains of PS or PB by 2-bromobutane during polymerization (Fig ure 2-13), anothe r equivalent of s -BuLi was added prior to monomer addition to give 3,4-dimethylhexane ( 2 ) as previously demonstrated (Figure 2-12).121,127,128 Indeed, the different possible secondary reactions that could happen during the halogen-lithium exchange reaction were previously studied.127,128 It was first demonstrated by gas chromatography analysis that aryllithiu m species are not nucleophilic enough to react with 2-bromobutane without the pres ence of polar additives such as tetramethylethylenediamine (TMEDA). Even in presence of TMEDA, this reaction is slow since only 10 % of 2-bromobutane is consumed after 90 minutes of reaction (Figure 2-13). Some other previous studies ha ve also shown that benzene when used as solvent can react with s -BuLi in presence of TMEDA to give th e corresponding phenyllithium species (Figure 2-13).129,130 The latter are able to initiate th e monomer polymerization to generate a multimodal distribution.131 The diadduct product 1 resulting from the reaction of 1 with s -BuLi took in cyclohexane a yellow color at the concentration of [Li+] = 5.3x10-2 M and a gelly aspect unlike the insoluble precipitate formed from the reaction of 4,4 -dibromobenzene with s -BuLi in the same solvent.121 The formation of such a physical ge l instead of a soli d precipitate is due to the presence of the C15 side alkyl ta il which helped preventing the irreversible precipitation of the dilithiated species.

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46 The halogen/lithium exch ange reaction between 1 and s -BuLi was thoroughly investigated by 1H and 13C NMR spectroscopy and mass spectrometry (Figure 2-14).The structure of the dilithium diadduct 1 was first confirmed by 1H (good integration values) and 13C NMR spectroscopy analysis of the product isolated after methanol quenching of a solution of 1 in cyclohexane ([Li+] = 5.3x10-2 M). Moreover, mass spectrometry analysis showed the total disappearance of the p eak of the dibromo precursor 1 (M = 538 g/mol) in favor of 1 with a principal peak at M = 381 g/mol after methanolysis (Figure 2-15). After checking the quantitative halogen/ lithium exchange reaction at this concentration ([Li+] = 5.3*10-2 M) and the truly difunctional in itiator structure, styrene or butadiene were polymerized by addition of the corresponding monomer (Figure 2-16). After introduction of a few monomer units the dili thiated species appear totally soluble in cyclohexane even in absence of stirring and of any polar additives. On deactivation of the living carbanionic chains by ethylene oxide after complete monomer consumption dihydroxy telechelic polymers were obtained from 1 Analysis by size exclusion chromatography (SEC) indicated the complete c onsumption of the initiator (Figure 2-17). No peak attributable to residual 1 could be detected in the lo w molar mass region, and the only trace seen was a narrow and monomodal peak co rresponding to the expected linear polymer in the high molar mass region (Figure 2-17). Such good control over the molar mass (good agreement between the experimental and theoretical values of molar masses ) and narrow molar mass distribution ( w M / n M <1.1) reflects a rate of initiation by 1 comparable to that of propaga tion (Table 2-1). The structure of the difunctional polymer formed could be established first by 1H NMR analysis using dihydroxy telechelic polybut adiene samples of low degrees of polymerization (Figure 2-18). From the ratio of the integration values due to the signal of the aromatic protons of the difunctional initiator ( = 6.5-7.5 ppm) to that of -C H2-OH chain ends ( = 3.7 ppm) the

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47 actual functionality of the sample s prepared could be determined: functionality values close to 2 were obtained for the polybutadiene telechelic s. Furthermore, the microstructure of the polybutadiene samples determined by 1H and 13C NMR spectroscopy (Figures 2-18 and 2-19) demonstrated a high percentage of 1,4-PB units (86-91%) in agreement with the fact that the polymerization occurred in an apolar solvent without any additives. This proportion of 1,4-PB units was almost half constituted of 1,4-cis a nd 1,4-trans (Table 2-1 and Figure 2-19), which is generally the case for linear polybutadiene synthesized using butyllithium as initiator in apolar solvents.15 After demonstrating the efficiency of this dicarbanionic initiator for the synthesis of polybutadiene telechelics with optimal elastomeric properties (high percentage of 1,4-PB units), SBS triblock copolymers were deri ved by sequential anioni c polymerization of butadiene (B), and styrene (S) with 1 as initiator (Figure 2-20). The initiation of styrene by polybutadienyllithium being slow compared to the reverse situation, it was necessary to dilute further the reaction medium with fresh cyclohexane and some THF (Cyclohexane/THF: 100/1 in volume). Upon introduction of styrene, the color of the medium changed instantaneously from the characteristic yellow color of polybutadienyllithium carbanions to the orange color of polystyryllithium carbanions. By taking an aliquot before the introduction of styr ene, the formation of the SBS samples could be easily followed by SEC (Figure 2-21). The absolute molar masses of the SBS triblock copolymers were deduced by 1H NMR spectroscopy knowing that of th eir polybutadiene precu rsor determined by SEC (Table 2-2 and Figure 2-22). In all cases narrow molar mass distributions were observed either for the polybutadiene precursor or for the triblock copo lymer structure with a complete consumption of the polybutadiene precursor during the polymer ization of styrene as attested by SEC with the disappearance of the polybutadie ne peak (Figure 2-21 ): this demonstrates that the growth

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48 of either the polybutadiene middl e block or the two polystyrene glassy end bloc ks occurred under living conditions. The mechanical properties, e.g., ultimate tensile strength and elongation at break, of the SBS triblock copolym ers containing small polystyrene end blocks (%wt (PS) < 35%) were also studie d to bring an other proof of the well-defined structure of these SBS triblock samples. As shown in Ta ble 2-2, excellent mechanical properties are obtained with ultimate tensile strength higher than 30 MPa and elongation at break of 1000% (Runs 10 and 11, Table 2-2) which are in good agreement with the mechanical properties generally obtained by SBS copolymers.132-135 2.4 Conclusion In summary, the halogen-lithium exchange reaction has been successfully applied to generate a new dicarbanionic initiator from a dibromoaryl compound. The presence of a C15 side alkyl tail in the dibromo precu rsor is essential to the solubili ty of the dilithiated initiator in apolar solvent. This is the first example of dilithiated species initiating efficiently anionic polymerization in absence of additive and affo rding well-defined polybutadiene telechelics with a high percentage of 1,4-PB units (91%).122,123 This initiator has proved to be very efficient in providing SBS triblock copolymers with excellent mechanical properties, e.g., ultimate tensile strength higher than 30 MPa and elongation at break of 1000%.122,123 A longstanding problem faced by the industry of styrenic thermoplastic elastomers for the last forty years could be worked out with the resu lts disclosed in th is contribution.

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49 Figure 2-1. Synthesis of SBS tribock c opolymer by sequential monomer addition. Figure 2-2. Synthesis of SIS triblock copolymer by coupling of living chains on dichlorodimethylsilane. C4H9Li+ H y drocarbon solvent C4H9CH2 CH CH2 CH Li n-1 Hydrocarbon solvent PSLi CH2CH CH CH2 PS CH2CH CH2 CH L i m-1 PSb -PBLi Hydrocarbon solvent PSb -PBCH2 CH CH2 CH Li n-1 (Lewis base) PSb -PBb -PSLi PSb -PBb -PSLi+CH3OH PSb -PBb -PS s -BuLi+ Benzene PS Li PSb -PI Li (CH3)2SiCl2(Li:Cl = 1.2:1) PSb -PIb -PIb -PS+PSb -PI Li 1. CH3OH 2. Fractionation (excess) PSb -PIb -PS (pure triblock)

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50 Figure 2-3. Synthesis of P(Sb t BAb -S) triblock copolymer by coupling of living chains on bis(bromomethyl)benzene. Figure 2-4. Synthesis of SB S triblock copolymer usi ng 1,3-diisopropenylbenzene as precursor. Figure 2-5. Synthesis of SBS triblock copol ymer using 1,3-di(1-phe nylethenyl)benzene as precursor. n -BuLi+ THF -78 C PS Li LiCl PS Li OC(CH3)3 O PSb -P t BA Li 2. CH3OHBr Br 1. PSb -P t BAb -PS +2 t -BuLi Cyclohexane/Et3N -20 C t Bu t Bu Li Li Cyclohexane / 25 C PB Li Li 1. 2. CH3OH PSb -PBb -PS 2 s -BuLi + Benzene C4H9 C4H9 Li Li Benzene / s-BuOLi PB Li Li / Benzene / THF 2. CH3OH 1. PSb -PBb -PS

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51 Figure 2-6. Complex diolefinic prec ursors used for the synthesis of organolithium diinitiators ( A 19,83, B 16, C 84, D 117, E M 17,82,118, N 119, O 120). CH2 nCH2 n CH2 n O CH2 n A B C D H G F E I J CH3CH3 H3C CH3 K L M N O O H2C CH 3 11

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52 Figure 2-7. Synthesis of SBS triblock copolymer from a dicarbanionic initiator formed by the reaction of lithium metal and -methylstyrene. Figure 2-8. Synthesis of P(EOb -Ib -EO) triblock copolymer fr om a difuncti onal initiator formed by the reaction of pota ssium metal and naphtalene. Li+ Toluene / THFH2CC CH3 Li H2CC CH3 Li 2 + H2CC CH3 CH2C CH3 H2CC CH3 CH2C CH3 Li Li H2CC CH3 CH2C CH3 CH2C CH3 Li H2CC CH3 Li or PSb -PBb -PS (Li+ -RLi+)(Li+ R Li+) 1. 2. +K K PI K K O 40 C PEOb -PIb -PEO K K CH3OH H+PEOb -PIb -PEO THF/-78 C

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53 Figure 2-9. Synthesis of 1-bromo-4-(4-bromophe noxy)-2-pentadecyl benzene ( 1 ). Br + O C15H31 K O C15H31 CuPow d e r yield = 57% Br2yield = 84% O C15H31 Br Br 1

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54 Figure 2-10. 1H and 13C NMR spectra (CD2Cl2, 400 MHz) of 1-bromo-4-(4-bromophenoxy)2-pentadecyl benzene ( 1 ).

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55 Figure 2-11. Mass spectrum of 1-bromo-4-(4-b romophenoxy)-2-pentadecyl benzene ( 1 ). Figure 2-12. Synthesis of a dicarbanionic initia tor by halogen-lithium exchange reaction using 1 as dibromo precursor. Br O Br C15H31 4 s -BuLi Cyclohexane R.T., 30 min O C15H31 Li Li1 1 + 2 2

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56 Figure 2-13. Secondary reactions resulting from the halogen-lithium exchange reaction. Li Li Li + PS Li TMEDA Benzene Br PS + LiBr H TMEDA Li Solvent Metalation Deactivation of the living chain ends Li + H Deactivation of the carbanionic sites Br Br TMEDA Insoluble Li +

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57 Figure 2-14. 1H and 13C NMR spectra (CD2Cl2, 400 MHz) of the addition product of 1 with sec -butyllithium obtained after methanolysis.

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58 Figure 2-15. Mass spectrum of the addition product of 1 with sec -butyllithium obtained after methanolysis. Figure 2-16. Synthesis of -dihydroxy telechelic polybutadiene from 1 Br O Br C15H31 4 s -BuLi Cyclohexane R.T., 30 min O C15H31 Li Li1 1 + 2 2 O C15H31 n n OH HO 3) CH3OH/HClO 1) 2) R.T., 24h

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59 Figure 2-17. SEC eluograms of (PS)2 difunctional polystyrene and (PB)2 difunctional polybutadiene : a) Protonated version of 1 ; b) Linear polystyrene (Run 2, Table 2-1); and c) Linear polybut adiene (Run 7, Table 2-1).

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60 Figure 2-18. 1H NMR spectrum (CD2Cl2, 400 MHz) of -dihydroxy terminated polybutadiene (Run 3, Table 2-1). Figure 2-19. 13C NMR spectrum (CDCl3, 400 MHz) of a -dihydroxy terminated polybutadiene (Run 6, Table 2-1).

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61 Figure 2-20. Synthesis of SBS triblock copolymer from 1 Figure 2-21. SEC eluograms monitoring the forma tion of a SBS triblock copolymer initiated in cyclohexane with 1 (Run 11, Table 2-2). Br O Br C15H31 4 s -BuLi Cyclohexane R.T., 30 min O C15H31 Li Li1 1 + 2 2 Cyclohexane, R.T., 24h PB Li 2 Bb -SLi 2 Cyclohexane/THF (100/1) R.T., 12h P O C15H31 CH3OH n n mm H H

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62 Figure 2-22. 1H NMR spectrum (CDCl3, 400 MHz) of a SBS triblock copolymer (Run 11, Table 2-2). Table 2-1. Characterization of PS an d PB samples synthesized from 1 difunctional initiator.[a] [a] Butadiene polymerization was initiated in cyclohexane with 1 ([Li+] = 5.3*10-2 M). [b] Determined by SEC in THF using a refractometric de tector. A conversion factor of 0.55 was used for the calculation of the PB molar mass. [c] n M(theo) = Mbutadiene x ([Butadiene]/[-PhLi]) x 2. [d] Calculated by 1H and 13C NMR. Microstructure (%)[d] Sample no. Polymer n M[b] w M / n M[b] n M(theo) [c] Yield (%) 1,4-cis 1,4-trans 1,2 1 PS2 11400 1.15 12000 97 2 PS2 43800 1.13 44000 98 3 PB2 2100 1.2 2000 98 38 47 15 4 PB2 6200 1.13 7000 98 39 47 14 5 PB2 16600 1.07 17000 99 39 47 14 6 PB2 43700 1.06 43000 98 40 50 10 7 PB2 51900 1.08 52000 97 40 50 10 8 PB2 67400 1.1 70000 98 41 50 9

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63 Table 2-2. Mechanical properties of SBS tr iblock copolymers initiated by 1 .[a] [a] Butadiene polymerization was initiated in cyclohexane with 1 ([Li+] = 5.3*10-2 M). [b] Determined by SEC in THF using a refractometric detector. A conversion factor of 0.55 was used for the calculation of the PB mola r mass. [c] Determined by 1H NMR from the molar mass of the polybutadiene block, assuming 100% efficiency in the initiation of the second block. PB2 SBS Sample no. n M[b] w M / n M[b] n M[b] n M[c] w M / n M[b] 1,4-PB[c] (%) Ultimate tensile strength (MPa) Elongation at break (%) 9 6200 1.13 20400 18300 1.2 86 10 43700 1.1 78300 60300 1.1 90 29.5 900 11 67400 1.1 110900 93500 1.2 91 33.8 1000

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64 CHAPTER 3 TRIAND TETRACARBANIONIC INITIATORS BY A LITHIUM/HALIDE EXCHANGE REACTION : APPLICATION TO STAR-POLYMER SYNTHESIS 3.1 Introduction Star-branched polymers represent the most simple polymer branched structures. A star-branched polymer consists of several linear chains linked together at one end of each chain by a single branch or junction point,136-138 in opposition to graft, dendrimer-like, and hyperbranched polymers. Among these star-branc hed polymers, three ca tegories of star polymers can be distinguished by the natu re and the lengths of their branches: Asymmetric stars with branches of sa me nature (i.e., same polymer), but different length.139,140 Mikto-arm stars which are constituted of polymer branches of different nature connected to the same core.139 (A)n (homopolymer) or (AB)n (diblock branches) stars connecting branches of same nature and length.140,141 We will be especially interested in this chapter by the (A)n and (AB)n star polymers. Star polymers are produced through three general synthetic r outes (Figure 3-1).141 The first also called arm-first method involves the synthesis of preformed arms followed by reaction with a multifunctional linking agent. The second route is a slight variation of the latter one, which sometimes is also termed the in-out method. This approach entails a coupling reaction of linear living chains with multifunctional agent such as divinyl compounds and a cross-over reaction to a second monomer to form star polymers. The third one is the core-first technique, which involves the use of a multifunctional initiator to initiate the polymerization of multiple branches of the star. Basically, the number of arms of the star polymer can be determined by the number of initiating sites. The latter approach is a major challenge since it requir es the prior design of well-defined multifunctional initiator.

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65 Furthermore, all the initiation site s must exhibit the same reactivity. However, anionic polymerization suffers from the lack of pl uricarbanionic initiator exhibiting precise functionality and good solubility. In comparison to controlled radical142 and cationic143 polymerizations where various plurifunction al initiators were described, only a few pluricarbanionic initiators c ould be successfully develope d in anionic polymerization.20,22 3.2 Literature Overview on (A)n and (AB)n Star Polymer Synthesis 3.2.1 Arm-first Method Two distinct strategies were used in this case. The first strategy involves the synthesis of living macroanionic chains and their subsequent reaction with a well-defined multifunctional electrophile, which acts as the linking agent (Figure 3-2). In such a case, the polymer chains possess e ither active centers (*) at their chain ends or functions capable of reacting with the antago nist functions (F) of the coupling agent. The required conditions for obtaini ng well-defined star polymers (i.e. low molecular weight distribution) are the precise f unctionality (number of functions F) of the coupling agent and the selectivity of the reac tion between active centers and the latter F functions. In some other cases, it was needed to comp ensate for the lack of deactivating linking agent of precise and higher f unctionality by the copolymeriza tion of the living macroanionic chains with a difunctional comonomer (divinyl diepoxide, etc). Th is second strategy was elaborated to access star polymers with a very high number of branches. The principle of the copolymerization of living chains with a difunc tional comonomer is illustrated in Figure 3-3. The grafting reactions on the pendant vinyl ic groupswhich can be in competition with the intramolecular cyclizat ionhas as a consequence on th e formation of a cross-linked core possessing a certain number of branches and affording by the fact a star structure. However, it is difficult to avoid the presence of residual linear chains because of the low reactivity of the pendant sites ( double bonds) towards active centers.

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66 3.2.1.1 Use of multifunctional coupling agent Several linking agents have been used for the synthesis of star polymers.15 The most important of those are chlorosilanes144 and chloromethyl or bromomethyl benzene derivatives.145,146 Chlorosilane compounds. The use of tetrachlorosilane as electrophilic coupling agent for the syntesis of four-armed PS stars wa s described for the first time in 1962 by Morton et al.144 Isomolecular polystyryllithium chains initiated by n -butyllithium were added on this tetrafunctional linking agent in hydrocarbon solvent. However, this reaction is not complete even in the presence of large excess of liv ing chains. The purification by a fractionation technique was needed in this case to separa te the four-arm from the three-arm stars. In 1965, Zelinski and Wofford147 also used the triand tetr achlorosilane derivatives for the synthesis of PB star polymers by deac tivation of polybutadienyllithium chains. In opposition to the results obtained for the polystyry llithium chains, the reaction is quantitative and lead to the formation of well-defined PB stars. The molecularweight data, the good correlation between the intrinsic viscosity a nd the molecular-weight, and the fractionation data allowed them to conclude to the complete stoichiometric coupling reaction between the polybutadienyllithium chains and this family of chlorosilane compounds. Fetters and Morton148 demonstrated in their case that the stoichiometric reaction of the polyisoprenyllithium chains with tetrachlorosila ne agent gives in majority three-arm stars. From these previous results, it appears that the grafting reaction efficiency varies as follow: polybutadienyllithium > polyisopren yllithium > polystyryllithium Since the observed evolution is in opposition to the evolution of the intrinsic reactivity of the living chains, it was concluded that only the steric hindrance ge nerated as the coupling reaction proceeds influences the reaction effi ciency. To remedy this problem and thus

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67 increase the yield of the coupling reactio n in the cases of polystyryllithium and polyisoprenyllitium chains, few butadiene units (average of five) were added before the reaction with the chlorosilane comp ound. By this way, Fetters and Morton148 were able to obtain in a quantitative manner four-arm PI st ar polymers using tetrachlorosilane as linking agent. Another way consists in th e use of compounds which have halogenated silyl groups separated by an alkyl chain. 1,2-bis(dichloromethyl silyl)and 1,2-bis(tr ichlorosilyl)ethane allowed Roovers and Bywater149,150 to synthesize and study a se ries of fourand six-arm PS stars. The addition of few isoprene units to the polystyryllithium chains allowed a considerable decrease of the time needed for the quantitative obtention of four-arm stars and was essential for the preparation of si x-arm stars. Hadjichristidis and Roovers151 used the same linking agents for the preparation of fourand six-arm PI star polymers. The synthesis of coupling agents of functi onality equal to 8, 12 and 18 was done by Hadjichristidis et al.152,153 by adapting the synthetic strategy for the obtention of the desired functionality (Figure 3-4). The efficiency of the coupling reactions betw een the latter polychlorosilane agents and polydienyllithium allowed the formation of well -defined star polymers with 8, 12, and 18 PI branches. It should be noted that the authors advocated the addition of butadiene units to increase the coupling reaction efficiency. By using this category of electrophilic agents, Toporowski and Roovers154 have obtained PS stars of 12 and 18 branches. In the latter case, some triethylamine was added to decrease th e coupling reaction time; indeed this additive allowed the increase of the carbanionic species reactivity in hydrocarbon solvents. These results confirmed that the reaction of chlorosilane derivatives with polymer chains possessing a butadi enylithium chain-end allowed the a ccess to well-defined structures and this even if the coupling agent functionality increases.

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68 To prepare star polymers of larg ely higher functionality, Roovers et al.155 had the idea to use as linking agent thirdand fourth-gen eration dendrimers possessing at their periphery chlorosilane groups of same reactivity.156,157 The dendrimers were prepared starting with tetravinylsilane and using two reactions, the h ydrosilylation of the vinylsilane groups with dichloromethylsilane and the nuc leophilic replacement of sili con chloride by vinylmagnesium bromide, as shown in Figure 3-5. PB stars of 32, 64 and 128 branches could be synthesized. However, it should be noted that the reaction for the prepara tion of 32and 128-arm star polym ers is very slow (8 weeks). These works generated the best results obtaine d in the area of the star polymer synthesis because of the very high number of branch es and the good definition of these structures. The use of methyltrichlorosil ane and tetrachlorosilane has also been extended to some other polymers. Ressia et al.158 thus demonstrated that it was possible to obtain threeand four-arm polydimethylsiloxane (PDMS) stars by using these coupling agents. In this case, fractionation is needed to separate four-a rm stars from three-arm stars. Mays and colleagues159 prepared three-arm poly(cyclohexadi ene) stars by deactivation of the corresponding living chains on th e methyltrichlorosilane. In 1989, an original method capable of generating PB star polymers of several hundred branches was described by the Roovers group.160 The synthesis took place in two steps. First, the 18-arm PB stars containi ng a large majority of 1,2-PB units were hydrosilylated to be modified into chlorosilane functi ons. In a second instance, polybutadienyllithium chains were deactivated on these latter chlorosilane groups. By using this strategy star polymers with an average of 270 branches were prepared. The coupling reaction is very slow and this even in the pres ence of triethylamine as additive. It is also impossible to precisely control the exact numbe r of branches obtained which depends on the yield of each of the two steps.

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69 More recently, Quirk and colleagues161 proposed a new methodology derived from the chlorosilane chemistry for the synthesis of star polymers utilizing the reaction of living polymers with alkoxysilyl-func tionalized polymers. After functionalization of a PSb -oligoPB polymeric organolithium compound with an ex cess of multifunctional chlorosilane linking agent (1,2-bis(dichloromethylsily l)ethane) in benzene, the re sulting polymeric chlorosilyl groups were converted to methoxysilyl groups with anhydrous methanol in the presence of triethylamine to minimize linking reactions. Fi nally, a four-arm star-branched polystyrene was prepared by treating methoxysilyl-functionalized PSb -oligoPB with excess of PSb oligoPBLi living chains (Figure 3-6). However, fr actionation is still needed to separate fourarm PS stars from the excess PSb -oligoPBLi. Halomethylbenzene compounds. The halomethylbenzene compounds is another category of polyhalogenated agents which were used for star synthesis. Yen and Wenger162,163 have demonstrated that the coupling reac tion between 1,2,4-trichloromethylbenzene and polystyryllithium species leads to a mixture of several populations, one corresponding to star polymers of functionality highe r than 3. The same procedure was also applied by Allen and colleagues164,165 for the four-arm star polymer synthesi s. For this purpose, the reaction was carried out in a mixture of THF/Benzene (50/ 50) at high temperature in the presence of 1,2,4,5-tetrachloromethylbenzene. In this case agai n, a mixture of polymer s with functionality in the range of 2 to 4 and even higher was obtained; the percentage of species with a functionality higher than the ta rgeted one was found around 40%. From these previous studies, it was concl uded that the low coup ling reaction yield and the formation of polymer with functionality higher than the theoretical one is due to a secondary reaction. This latter is the hal ogen-lithium exchange reaction described below (Figure 3-7).

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70 This parasitic reaction generates in the re action medium on the one hand chloridefunctionalized polystyrene chains and on th e other hand a second carbanionic species (RMetClX-1). The latter species can th en react on the halide f unction of the coupling agent (RClX) and thus lead to the formation of a coupling agent of higher functionality, polystyryllithium chains being capable of reac ting again with this new linking agent. Altares et al.165 demonstrated that the coupling agent should be added on the polystyryllithium chains and not the reverse. Processing in this way, only 7 % of the fi nal product was contaminated by star polymers of functionality higher than the expected one. When carried out in dry THF, Bryce et al.166 deactivated polystyryllithium chains in 1,3,5-trichloromethylbenzene. Meunier and Van Leemput167 also used the same conditions in the case of 1,2,4,5-tetrachloromethylbenzene a nd hexakis[p-(chloromethyl)phenyl]benzene. In the latter cases, the star sa mples did not show any species of functionality higher than the targeted one. The use of THF allowed the e limination of the halogen-lithium exchange reaction. The same observation was reported by Ye n who worked with potassium as counterion.163 As described by Bryce et al. ,166 the use of 1,3,5-tribromomethylbenzene does not allow the preparation of PS stars. They demons trated that this reaction leads only to the formation of a difunctional polymer. Howe ver, the multifunctional bromobenzene compounds proved to be more efficient for some other polymers. Indeed, Pitsikalis et al.168 recently used tetrabromomethylbenzene for the preparation of poly(2-vinylpyridine) (PVP) and poly(methyl methacrylate) (PMMA) stars (Figure 3-8). Th e deactivation reaction of the corresponding living chains in THF at low temperature leads to the formation of four-arm stars. Other fourand six-arm stars were synthesized by Lazzari et al.169 who resorted to 1,2,4,5tetrakis(bromomethylbenzene) and hexakis(bromomethyl)benzene as coupling agents (Figure 3-8).

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71 This arm-first method was also applied by Mllen and colleagues170 for the synthesis of core-shell nanoparticles consisting of a sh ape-persistent polyphenyl ene dendrimer as the core and of different polymers PS, PI, PEO as monoor double-shells. For example, monoshell systems were obtained by grafting-onto (arm-first) pro cess attaching PEO chains to a second-generation polyphenylene dendrimer with an average of 12 chloromethyl functions. Well-defined PEO-functionalized polyphenylene dendrimers with molecular weights between 104 and 106 Da were prepared. Phosphonitrile chloride compounds. Some other research groups turned towards an other category of multifunctional electroph ilic compounds. For example, Gervasi and Gosnell171 compared the coupling reaction efficiency of polystyryllithium chains with cyclic trimer phosphonitrile chloride in the first case a nd bis(trichlorosilyl)etha ne in the second one. The first coupling agent allowed the formation of six-arm stars, whereas the second one gives at best four-arm stars. These results could be surprising when compared with that of Roovers et al.172 However, the experimental condi tions used by Gervasi and Gosnell171 are different since they did not add any additives and used a mixture of polar/apolar solvent which changes the reactivity of the polystyryllithium species. Multifunctional fluorinated coupling agent. More recently, Bates and colleagues173 have investigated, a simple, unique method fo r star polymer synthesis. Living anionic polyisoprene (PILi) chains were terminated by addition of hexafluoropropylene oxide (HFPO). Through a series of fluoride ion (F-) eliminations (creating carbonyl groups) and nucleophilic attacks by additional PILi chains, each molecule of HFPO coupled three chains, forming regular three-armed stars (PI3) (Figure 3-9). The authors claimed that this strategy eliminates the need for fractionation (in contra st to chlorosilane system) of the resultant polymer since unreacted homopolymer and twochain coupling products are negligible under appropriate reaction conditions. However, complete coupling of PILi chains was never

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72 observed using arm molecular weights higher than 5 kg/mol. Indeed, for larger molecular weights, uncoupled PI chains and two-chain coupling products were observed by SEC. Unsaturated multifunctional compounds. Allyloxy based compounds. Herz and Strazielle174 were the first to employ allyloxy-base d compounds, such as tri-(allyloxy)-2,4,6-striazine (TT), as deactivating ag ent. After checking the efficiency of this latter linking agent on the case of small organometallic mol ecules, this reaction was extended to polystyrylpotassium chains. This method allowe d the formation of three-arm PS stars with narrow molecular wieght distribution. However, the presence of small quantity of linear PS chains deactivated by impurities could not be complete ly avoided. By reaction of TT with the tetraphenyl diisobutane, the same authors175 obtained a tetrafuncti onal coupling agent which result in the formation of four-arm star polymers. Unsaturated multifunctional compounds. DDPE-type derivative. 1,3,5-Tris(1phenylethenyl)benzene was used by Quirk and Tsai20,176 as a linking agent for the synthesis of a three-arm PS star, as shown in Figure 3-10. SE C and light scattering (LS) results showed that the reaction is stoichiometric and complete leading to a well-defined star. Despite the fact that the arm molecular weight used was rather low ( Mn = 8.5 x 103 g/mol), it can be concluded that there is no steric limitation for the synthe sis of three-arm PS star s using this coupling agent. Previous efforts to use methyltrichlor osilane as a linking agent for the synthesis of three-arm PS stars were not successful, due to incomplete coupling (ste ric hindrance effects). Unsaturated multifunctional compounds. Fullerene. Soon after the discovery of fullerenes, efforts were made to use C60 as a coupling agent for the preparation of star polymers. Samulski et al.177 reported the reaction of living polystyryllithium chains with C60, and later Ederl and Mathis178 extended this work, providi ng mechanistic aspects on this reaction in different solvents. In a nonpolar solvent su ch as toluene, it was found that by using an excess of living PSLi chains over C60 a six-arm star can be prepared by addition of the

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73 carbanions onto the double bonds of fullerene. A similar behavior was observed when living polyisoprenyllithium was used fo r the coupling reacti on. In polar solven ts such as THF a different situation was observed. During the reaction of a livi ng polystyrylpotassium with C60 in THF, a two-electron transfer was initially observed followed by the addition of four chains, according to Figure 3-11. However, in both types of solvents, the func tionality of the product could be adjusted by changing the reactivity and/or the steric hi ndrance of the living chain end. Thus, when the living PS chains were end-capped with one un it of diphenylethylene (DPE), only the threearm star was produced. The functionality could be also controlled by th e stoichiometry of the reaction between the living polymers and C60. However, it was impossible to selectively incorporate one or two chains per C60 molecule. 3.2.1.2 Copolymerization with a divinyl compound Divinylbenzene. The copolymerization between a difunctional monomer and living anionic polymer chains is also another way to get star polymers with a large number of branches. First considered by Milkovich,179 Rempp and colleagues180 described the synthesis of star polymers by anionic copolymerization of styrene and divinylbenzene (DVB). Thus, these star polymers are constituted of a cross-linked polydivinylbenzene core linked to several PS chains which ensure the star solubilizatio n. However, by using th is way, star polymers with large molecular weight di stribution have been obtained.181 Moreover, the star polymer samples were spoiled by a non-negligible quantity of linear PS indicating that the reaction between living linear chains and double bonds was less probable as the polyDVB central core is growing. This process led also to the same results when app lied to the PI star synthesis182 : a large molecular weight distribution and th e presence of linear chains. In 1969, Worsfold183 were able to obtain a more homogeneous molecu lar weight distribution for the star polymers by using a pur paraor meta-DVB co mpound and benzene instead of THF.

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74 However, it is still difficult to predict th e number of branches linked to the polyDVB core. All the previous studies demonstrated that the number of branches is dependent on numerous parameters. Besides th e ratio R = [DVB]/[Living chains], the length of the chain precursors, the nature of the solvent (THF or benzene),183 the stirring conditions,184 the purity and the composition of DVB,23 the temperature,185 and the chemical nature of the living chains (styrene,183,186,187 butadiene,185,188 or cyclohexadiene189), could influence the copolymerization reaction and at the same time the star preparation. In conclusion, DVB is certainly useful for th e preparation of star polymers of different chemical nature and the coupling reactions are efficient for R values higher than 4. Even though this method allowed the formation of star polymers with a number of branches varying in a large range in function of the ratio R,184,185,187,188,190-192 this is still impossible to obtain well-defined structures. Ethylene glycol dimethacrylate. Ethylene glycol dimethacrylate (EGDM) was also used as comonomer for the plurifunctional crosslinked core synthesis, especially in the case of PMMA stars. Indeed, in th is latter case, the us e of DVB and chlorosilane compounds is unthinkable because of the low reactivity of th e PMMALi living chains. The first example of EGDM use was proposed by Zilliox et al.182 who obtained PMMA star samples with large molecular weight distribution. More recen tly, the same EGDM comonomer allowed Efstratiadis et al.193 to prepare PMMA stars with a bette r structure definition, but only for arm molecular weight higher than 40 kg/mol. Below this value, intermolecular coupling reactions between different stars occured giving sample s with large molecular weight distributions. Researchers from DuPont194,195 proposed, in their case, th e synthesis of PMMA stars by group transfer polymerization (GTP) usi ng PMMALi living chains and EGDM as comonomer at 85 C. The same comonome r was employed by Helder and Mller196 for poly( t -butyl acrylate) (P t BuA) star synthesis.

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75 However, as for the case of DVB, all the studies182,193,195 result in the same conclusions, that is namely the number of branches in the star polymers depends on : length of the living chains the ratio [EGDM]0/[Living chains]0 reaction time of the living chains on the difunctional comonomer. Moreover, the quantity of residual linear ch ains is decreasing with the polymer chain length and increasing with the r eaction time and the ratio [EGDM]0/[Living chains]0. For example, the reaction of isotactic PMMALi living chai ns, initiated by t butylmagnesium bromide in the presence of 1,8-diazabicyclo[5.4.0]undec-7ene, with EGDM comonomer led to the formation of star pol ymers with a number of branches estimated between 20 and 30.197 In the case of syndiot actic PMMALi, Hatada et al.197 advocated the use of butane-1,4-diol in place of EGDM to make easier the coup ling reaction (obtention of star polymers with number of branches ranging from 50 to 120). 3.2.2 Core-first Method In this second method a multifunctional orga nometallic compound, that is capable of simultaneously initiating the polymerization of se veral branches, is used in order to form a star polymer (Figure 3-12). There are several requirements that a multifunctional initiator has to fulfill in order to produce star polymers with uniform arms, low molecular weight distribution, and controllable mo lecular weights. All the initiation sites must be equally reactive and have the same rate of initiation. Furthermore, the initiation rate must be higher than the propagation rate. Only a few multifuncti onal initiators satisfy these requirements, and consequently, this method is not very succ essful. Complications often arise from the insolubility of these initiators, due to the st rong aggregation effects. The steric hindrance effects, caused by the high segment dens ity, causes excluded volume effects.

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76 3.2.2.1 Multifunctional oxanionic initiators These plurifunctional initiators posse ss hydroxyl functions which can, once deprotonated, initiate the polymerization of ox irane monomers in a more or less efficient way as shown by the different examples below. The first example of PEO stars was reported in the literature by Gnanou et al.198 in 1988. In this paper, the authors propose thre e different methods to prepare PEO stars. The first strategy results from the deprotonation of hydroxyl functions of trimethylolpropane. The successive metalation of the alcohol groups has as consequence the decrease of the precursor solubility. Indeed, once all the hydroxyl f unctions are deprotonated, the multioxanionic species are totally insoluble. However, the addition of ethylene oxide in the reaction medium leads to the fo rmation of three-arm PEO stars. The second one consists in the synthesis of a graft copolymer which can be considered as a star polymer, if the penda nt chains are largely longer than the polymer backbone. For this purpose, potassium 2-alkoxide ethyl styrene was first polymerized to build the backbone. In a second step, the alkoxide sites were used as in itiators for the ethylen e oxide polymerization. The average number of PEO side chains obtained is close to 25. The last method proposed consists in the reaction of naphtalene potassium with a difunctional monomer such as DVB to form a microgel nodule covered by living anionic sites which can be used as a multifunctional initiator. The ratio [DVB]/[K+] should be kept lower than 3 in order to reduce the aggregation and to avoid a network formation. PEO stars having 4, 8, and 16 arms were al so prepared using hydroxyl-functionalized carbosilane dendrimers of several generations.199 For this purpose, the end groups of a chloride-functionalized carbosilane dendrimer were converted to hydroxyl groups and were activated using potassium naphthalene. The polym erization of ethylene oxide was initiated by these active sites. The re sults of these methods confirmed th e preparation of well-defined star

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77 polymers with narrow molecular weight distributi ons. However, the tedious preparation of the dendrimer core molecules is th e only drawback of this method. Hyperbranched polyglycerol and polyglycerol modified with short poly(propylene oxide) chains, activated with diphenylmethylpotassium (DPM K), were also employed as multifunctional initiators for the synthesis of PEO stars.200 Hyperbranched polyglycerol was found to be an unsuitable initiator due to the strong association effects caused by its highly polar groups. The incorporation of the poly(propylene oxide) chains (degree of polymerization, 23 52) was crucial for the synthesis of the PEO stars. Moderate to large molecular weight distributions were obtained ranging from 1 .4 up to 2.2. The functionalities of these stars were calculat ed to vary between 26 and 55. Second-generation polyphenylene dendrimer s functionalized w ith exactly 16 hydroxymethyl groups prepared by the Mllen gr oup were also used as multiinitiator for the living anionic polymerization of ethylene oxide to obtain well-defined core-shell nanoparticles.170 3.2.2.2 Pluricarbanionic initiators This category of multifunctional initiators, especially used for the polymerization of vinyl and diene monomers, was not really successfull compared to the multifunctional initiators used in the other polymerization t ype such as radical co ntrolled polymerization (ATRP, RAFT, NMP, etc).142 The tedious synthesis of pr ecursors of higher functionality and the low solubility of the pluricarbanionic species in different solvents are the main reasons of this lack of interest. Moreover, even when the latter were soluble, the results obtained after polymerization were in most cases disappointing. The different examples of pluricarbanionic in itiators reported in the literature were already discussed earlier (Chapt er 1). The only convincing ex ample is the synthesis of a tricarbanionic initiator proposed by Quirk and Tsai.20 This multifunctional initiator, was found

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78 soluble in apolar solvents after reaction of 3 moles of sec -butyllithium with 1,3,5-tris(1phenylethenyl)benzene (tri-DPE) as presente d in Figure 1-2. The efficiency of the tricarbanionic species was demonstrated for the anionic polymerization of styrene and butadiene, but always in the presence of polar additives to avoid the formation of polylithiated species aggregates.20,21 3.2.2.3 Polythiolates initiators Nicol et al.201 have first reported the synthesis of sulfur-containing star polymers by anionic polymerization of propylene sulfide in itiated with multifuncti onal thiols in the presence of 1,8-diazabicyclo[5,4,0] undec-7-ene (DBU) as the co-i nitiator. However, the lack of diversity in multifunctional thiol structures, which originates from oxidative coupling to form disulfides, reduces versatility in designing star poly(sulfide)s. Endo and colleagues202 proposed in their case a nov el trifunctional initiator synthesized by reaction of a five-membered cy clic dithiocarbonate with benzylamine or octadecylamine (Figure 3-13). The initiator system was cons tructed by addition of DBU, which leads to the thiolates/thiols equilib rium through rapid proton exchange. Anionic polymerization of propylene sulf ide using trifunctiona l initiator/DBU system was carried out in dimethylformamide (DMF) at 0 C and was quenched by 1-(chloromethyl)naphtalene, which has been to be effective for termina tion of thiirane polymerization. The trifunctional initiator efficiently initiated the polymeri zation of propylene su lfide to afford the corresponding star-shaped polymers quantitatively with narrow molecula r weight distribution. 3.2.3 In-Out Method This method consists in resorting, in a first time, to the core-first method to generate carbanionic sites, which could in a second instance initiate the polymerization of the same or another monomer introduced in the reaction medium.27,187,191,203-207

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79 Zilliox et al.181 were the first to employ this strate gy. Indeed, after the preparation of a stable polyDVB suspension by addition of PSLi chains on DVB, another styrene aliquot was added in the reaction medium. However, large mo lecular weight distributions were obtained for the different star samples and the control over the number of branches was not reliable. In order to improve the control over the star structure by using this In-Out method, Quirk et al.208 replaced DVB by a diphenylethylene derivative and studied the coupling reaction of PSLi living chains with 1,3-bis( 1-phenylethenyl)benzene (MDDPE) followed by the initiation of styrene polymerization by the carbanionic sites generated after the coupling step (Figure 3-14). The coupling reaction of poly(styryllithiu m) of various molecular weights with MDDPE in benzene is a very efficient reaction when the stoichiometry of the reaction is carefully controlled (yield > 96%). Because of the lack of reactivity of poly(dienyllithium) chains in addition reactions w ith 1,1-diphenylethylen e units, it is necessary to add a small amount of Lewis base such as THF for the formation of (PB)2-MDDPE targeted product. After addition of a second amount of monomer, calculated to obtain the same monomer unit number as for the initial branches, a four-arm PS star is obtained. Through their studies, they demonstrated that the addition of Lewis base such as THF and s-BuOLi is needed during the crossover reaction to preven t chain-end association beha vior for these dilithium macroinitiators in hydrocarbon solvent. Moreover, a minimum arm lengths of 3x103 g/mol (value determined by UV-Vis spectroscopy st udies) is required for complete crossover reaction of diphenylalkyllithium sites with st yrene monomer. By comparing the samples prepared with the ones obtained by coupling reaction with SiCl4, Quirk et al.208 could conclude to the four-arm stru cture of the star polymers synt hesized by this In-Out method.

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80 3.2.4 In-In Method The basis of the two-step In-In method209,210 is as follows: star polymers with polyDVB cores, synthesized by the arm-firs t method, include many unreacted double bonds in their cores, and these double bonds can be attacked by the carbanions of some monomers such as styrene and dienes (Fig ure 3-15). Therefore, in the firs t step of this method, a starshaped polymer with a polyDVB core is synthe sized in the same way as an arm-first method. In the second step, a known amount of the star polymer synthesi zed in the previous step is dissolved in THF and added to living PS or polydiene chains. Th e carbanions located at the end of the living linear chains attack the double bonds of the cores of the star molecule and attach to them by reacting with these double bonds. However, for some monomers such as alkyl methacrylate, vinyl pyridin e, and ethylene oxide, which have higher electrophilicity than styrene or divinylbenzene, the carbanions of these monomers cannot attack the double bonds of the cores of the star molecules. 3.3 Results and Discussion 3.3.1 Application of Halogen-Lithium Exchange Reaction to Star Polymer Synthesis We have exploited here the possibilities offered by this halogen-lithium exchange reaction to prepare novel triand tetracarbanionic ini tiators for the synthesis of well-defined threeand four-arm star polymers obtained by the core-first method.121 This method rests on the metallation of poly(aryl halide)s whose halogens are car ried by separate aryl rings. Unlike regular halogen-metal exchanges, the me tallation in our case could be conducted at room temperature and in apolar medium for the polylithiated species formed, which were unexpectedly found soluble in the presence of / -coordinating ligands; this remarkable feature could be further expl oited for star synthesis. To successfully demonstrate the viability/per tinence of our method, we have utilized a commercially available diaryl halide ( 1 ) and have also designed two poly(arylhalide)s carrying respectively three ( 2 ) and four ( 3 ) halides. The two poly(arylhalide)s of functionality

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81 3 and 4 have been obtained using reported proc edures (see Chapter 7: Experimental Part).211213 2 was derived from the reaction of 4-bromoa cetophenone diethyl ketal with acetyl chloride using samarium trichloride as catalyst; as for 3 it was generated in excellent yields ( 90%) by Diels-Alder reaction between 2,3,4,5-tetrak is(p-bromophenyl)-cycl opentadienone and phenylacetylene, carbon monoxide being extruded in th is process. The expected structures of the different multibromo compounds were demonstrated by 1H NMR spectra of 2 and 3 (see Chapter 7: Experimental Part). Next 1 2 and 3 were subjected to reaction w ith stoichiometric amounts of sec butyllithium in benz ene to generate 1 2 3 the corresponding di-, tr i-, and tetracarbanionic initiators (Figure 3-16). The formation of 2-bromobutane ( 4 ) which accompanies these reactions was monitored by gas chromatography (GC) (see Chapte r 7: Experimental Part). In the three cases the yields were quantitative as only 2-brom obutane and the corresponding protonated polyaryl compounds were found in the analyzed produc ts. No coupling between 2-bromobutane and the pluricarbanionic species formed, 1 2 or 3 was ever detected, indicating that in apolar medium no such side reactions occurred. Howeve r, the resulting polylithiated species were insoluble in benzene and therefore could not be used as such for initiation purpose, the monomers triedstyrene, butadiene, 1,1-diphe nylethylenefailing to react with these aggregates. Various additives have thus been employed to solubilize these pluricarbanionic species. Even though tetramethylethylenediamine (T MEDA) was able to so lubilize the diand tetralithiated initiators, out of the additives trie d the ligand that proved the most efficient at solubilizing these carbanionic aggregates no matter their functionality was lithium 2methoxyethoxide ( 5 ) (Figure 3-17); this / -ligand was previously employed by Teyssi and colleagues214 to prevent lithium enolates from aggr egating in apolar medium and by this means bring about livingness in the anionic polym erization of methacrylic monomers. A ratio

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82 of [lithium 2-methoxyethoxide] to [-PhLi] equa l to 4 was necessary to obtain fully soluble initiators in benzene (Fi gures 3-17 and 3-18). In thes e attempts at solubilizing 1 2 3 5 was prepared separately by reaction of sec -butyllithium with 2-methoxyethanol, but in the polymerization experiments conducted subsequently 5 was simply generated in-situ by addition of sec -butyllithium prior to the lith ium-halide exchange undergone by 1 2 or 3 (Figure 3-18). Before triggering polymerization by mono mer addition, we managed to neutralize 4 that resulted from the lithium-halide exchange reaction; even though 4 was inert enough not to react with 1 2 and 3 the poly(aryllithium)s formed, it is sufficiently electrophilic to deactivate the growing carbanionic chains of pol ystyrene or polybutadiene. Indeed, in a separate experiment conducted under stoichiometric conditions and in benzene we observed the occurrence of such deactivation of polystyryllithium anions by 4 in the presence of TMEDA, the disappearance of 4 being complete in less than thirty minutes. To neutralize 4 prior to monomer addition one equivalent of sec -butyllithium was added and the formation of 3,4-dimethylhexane ( 6 ) that resulted was monitored by GC (see Chapter 7: Experimental Part). The disappearance of 4 and the concomitant formation of 6 were monitored by gas chromatography (GC) with tra ce of undecane as internal sta ndard. After checking that the neutralization of 4 was complete, the polymerization of styrene or butadiene could be triggered upon addition of the corresponding monomers. Upon deactivation of the living carbanionic chains by ethylene oxide af ter complete monomer consumption, -hydroxyl threeand four-armed polystyrene and pol ybutadiene stars could be isolated from 2 and 3 used as initiators (Figure 3-18). -dihydroxyl telechelic samp les were obtained from 1 Analysis by gas chromatogr aphy and size exclusion chro matography (SEC) indicated the complete consumption of initiators. No peak attributable to the presence of residual 1 2 or 3 could indeed be detected in the low molar mass region, the only trace seen being a

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83 narrow and monomodal peak corres ponding to the expected star or linear polymer in the high molar mass region (Figure 3-19). Such a narrow molar mass distribution ( w M / n M <1.1) reflects a rate of initiation by 1 2 or 3 comparable to that of propagation (Table 3-1). The structure of the polymer formed and specially the star character could be established first by 1H NMR analysis using polybutadiene samples of low degr ees of polymerization (Figure 3-20). From the ratio of the integration values due to the signal of the aromatic core ( = 6.8-7.3 ppm) to that of -C H2-OH chain ends ( = 3.7 ppm) the actual functi onality of the various sa mples prepared could be determined: functionality values close to 3 and 4 were respectively obtained for the threeand four-arm polybutadiene stars and cl ose to 2 for the telechelics. Characterization of both linear and star polystyrene and polybutadiene samples by SEC equipped with a light-scattering detector (S EC-LS) also showed an excellent agreement between experimental and expected values of molar masses. Further evidence of the threeand four-arm star structure could also be obtained by comparing the intrinsic viscosity [ ] of our samples with that of linear polymers. Indeed, one classical means to probe star-like architectures an d their actual functionality is to determine g which represents [ ]star/[ ]linear. As can be seen in Table 3-1, the g values calculated are close to the ones predicted by theoretical models.215-217 These results thus confirm that the structures initially targeted were actually obt ained and validate the pertinence of our novel approach of star synthesis by anionic means. After demonstrating the efficiency of these di-, triand tetracarba nionic initiators for the synthesis of polystyrene and polybut adiene telechelics and stars, (ABC)n (with n = 2, 3 or 4) linear and star block terpolymers were de rived by sequential anionic polymerization of styrene (S), butadiene (B) and methyl methacrylate (M) using 1 2 or 3 as initiators. These novel architecturesP(Sb -Bb -M)2 pentablock from 1 P(Sb -Bb -M)3 and P(Sb -Bb -M)4

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84 star block terpolymers from 2 and 3 respectivelywere actually prepared by the same sequence of monomer addition as for the synthesis of P(Sb -Bb -M) linear block terpolymers (Figure 3-21).218 Since lithium 2-methoxyethoxide ( 5 ) was present as an additive to solubilize 1 2 or 3 methyl methacrylate could be polymeriz ed under living conditionsas disclosed by Teyssi and colleagues214from polybutadienyllithium anions. Prior to the addition of M polybutadienyllithium anions were end-capped with 1,1-diphenylet hylene (DPE) to reduce the probability of side reactions on the ester group of M while initiating its polymerization. The reaction medium was also diluted with tert -butylbenzene and the temperature decreased to 40C to further prevent the above mentioned si de reactions. Upon addition of M, the medium turned from red characteristic of diphenylethy llithium carbanions to colorless. An aliquot being sampled out before introduction of each t ype of monomer, the formation of these SBMbased architectures could be easily followed by SEC (Table 3-2 and Figures 3-22 and 3-23). The absolute molar mass of the first PS bl ock could be obtained by SEC-LS; as for PB and PM blocks their respectiv e molar masses were deduced by 1H NMR spectroscopy knowing that of their precursor (Table 3-2, Fi gure 3-24). In all cases narrow molar mass distributions were observed for the three types of structures, attesting th at the growth of the three blocks occurred under living conditions. In some instances, P(Sb -Bb -M)n star block terpolymers were contaminated with P(Sb -B)n precursors (less than 10%) but the latter could be easily removed by fractiona tion through silica column. 3.3.2 Synthesis of Amphiphilic Star Block Co polymers Based on Polybutadiene and Poly(ethylene oxide) We present here the fi rst synthesis of (PBb -PEO)n (n = 3 or 4) amphiphilic star block copolymers based on a polybutadie ne core and poly(ethylene oxide) corona by anionic polymerization.219 The divergent or core-first method ap pears to be the best route to prepare such materials. The convergent method w ould require the synthesis first of PEOb -PB-Li+

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85 linear living chains with a first block of PEO and a second block of PB, which is not known to date. The only attempt to synthesize PBb -PEO block copolymer with complex architecture was the work of Xu and Zubarev,220 who prepared 12-arm PBb -PEO heteroarm or miktoarm star copolymers by the coupling of V-shaped PBb -PEO chains to an aryl ester dendrimer core; these were certainly not star block copol ymers containing PEO blocks at the corona and PB blocks at the core as in our case so that both bulk and soluti on properties would be different. Previously, we presented the synthesis of novel triand tetracar banionic initiators based on a halogen-lithium exchange reaction an d the example of well-defined three and fourarm polystyrene and polybutadiene st ars obtained by the core-first method.121 The preparation of (PBb -PEO)n (n = 3 or 4) star block copolymers begins with the transformation of the hydroxyl end groups in the (PB-OH)n (n = 3 or 4) star polymers (Figure 3-25). For this purpose, two star-shaped polybutadiene precursors were used as macroinitiators for the PEO pol ymerization (Table 3-3). The polybutadiene stars were first purified by freeze-drying in benzene or di oxane, and then reacted. A solution of diphenylmethylpotassium (DPMK) in THF of k nown concentration, was then added dropwise over a colorless solution of a known amount of (PB-OH)n (n = 3 or 4) in anhydrous THF to titrate the hydroxyl end groups. At stoichiometr y, a color change of the solution depending on the initiator concentrations is observed. The m acroinitiator solutions ar e green, red or yellow for initiator concentrations of 1.5x10-3M, 6.25x10-4M or 3.15x10-4M, respectively. In addition, the amount of (PB-OH)n (n = 3 or 4) macroinitiator, calcu lated from the molecular weight and the mass of polybutadiene stars introduced in the fl ask, was used to confirm that such titrations with DPMK were quantitative. After titration, et hylene oxide was added to the (PB-O-K+)n (n = 3 or 4) macroinitiator solution as a liquid at C and the solutio n immediately became colorless. Then the reaction mixture was heated to 45 C and the polym erizations were typica lly run for 3 days to

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86 ensure complete conversion of ethylene oxide Deactivation of the living chains was accomplished by the addition of acidic methanol (MeOH/HCl). Potassium chloride salts (KCl) precipitated upon termina tion were isolated from the hydroxyl-terminated star block copolymers by filtration. After concentration of the (PBb -PEO)n (n = 3 or 4) solution on the rotary evaporator, the block copolymers were precipitated in MeOH for the short PEO blocks and in ethylic ether for the long PEO bloc ks and finally dried under dynamic vacuum. All the data for the (PBb -PEO)n (n = 3 or 4) star block copolymers are summarized in Table 3-3. The recovered polymers were weighe d, and the high yields demonstrate that the conversion of ethylene oxi de was near quantitative in all cases. Knowing the molar mass of the PB core estimated by SEC/LS, the actual molar masses of the star block copolymer has been determined by comparing the resonance signal at = 3.6 ppm ((OCH2CH2)n (PEO block)) with that at = 4.8-6.0 ppm (protons of the double bonds (PB block)) (Figure 3-26). A good agreement was found between the theore tical and experimental molar masses as shown in Table 3-3. The apparent molar mass values and polydispersity indices for the (PBb -PEO)n (n = 3 or 4) block copolymers were measured by SEC in THF (Figure 3-27). A shift to high molar masses with the disappearance of the (PB-OH)4 precursor peak (see (PB76b -PEO1725)4), a good control over the PEO molar masses and the relatively narrow polydispersities ( Mw/ Mn<1.32) indicate that the block copolymer s obtained are free of any PB-OH star precursors demonstrating that all hydroxyl groups of the (PB-OH)4 star polymer were deprotonated during the deprot onation step and that the al koxides formed initiated the polymerization of ethylene oxide. The broadening of the molar mass distribution after the EO polymerization merely results from the fact that some alkoxides have a tendency to form aggregates in equilibrium with unaggregated alkoxides.221

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87 However, it can be seen that as the PEO molar mass per arm in (PB76b -PEO444)4 and (PB76b -PEO1725)4 increases molar mass distribution na rrows with a symmetrical SEC trace for the (PB76b -PEO1725)4 sample. In addition, we did not detect any amount of PEO linear homopolymer (which could result from a slight excess of DP MK in the reaction mixture) even in the case of the sample s with longest PEO blocks ((PB76b -PEO444)4 and (PB76b PEO1725)4) : they were indeed precipitated in diet hyl ether and the presence of linear PEO was never observed which would have been totally in soluble in diethyl ether as well. The same observations were made in the case of the three-arm star block copolymers. The amphiphilic character of the (PBb -PEO)4 star block copolymers was first demonstrated by 1H NMR spectroscopy in CD2Cl2 and CD3OD (Figure 3-28). Figure 3-28A shows the resonance signals of both the hydrophobic and hydrophilic blocks in solution in CD2Cl2, whereas Figure 3-28B shows that only th e resonance signals corresponding to the PEO hydrophilic block are observed in CD3OD solution. The latter obs ervation is consistent with previous literature results that demonstrate CD3OD is a good solvent for PEO blocks and a non-solvent for PB blocks and as a consequence the formation of amphiphilic micelles in CD3OD with the PB core hidden by the PEO branches.222-224 3.4 Conclusion In summary, halogen-lithium exchange reactions have been successfully applied to generate di-, triand tetracarbanionic species from bis-, trisand tetrabromoaryl compounds. The use of a / ligand was instrumental in obtaini ng polycarbanionic init iators soluble in apolar medium and the subsequent prepara tion of various well-defined star-shaped (co)polymers. These are the first examples of three and four-armed polystyrene and polybutadiene stars obtained by the socalled core-first method using anionic polymerization.121 Analysis of the macromolecular arch itectures obtained by different means including SEC-LS, 1H NMR spectroscopy and viscometry all endorse the star character and a

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88 functionality of 3 and 4 for the samples derived from 2 and 3 respectively. The efficiency of the latter was even exploited to synthesize (PBb -PEO)n amphiphilic star block copolymers219 and P(Sb -Bb -M)n star block terpolymers (n = 3 or 4).121 The phase separation and morphologi es that develop in such P(Sb -Bb -M)n star block terpolymers could be investigated and comp ared with those reported for linear SBM copolymers.225 Moreover, the good definition of the (PBb -PEO)n amphiphilic star samples allowed us to study their behavior either in aqueous solution or at the air/wa ter interface. Figure 3-1. General strategies fo r star polymer synthesis. X Living Polymerization Multifunctional Initiator + *Multifunctional Coupling Agent Coupling Reaction + Y 1) Linking Reaction 2) Living Polymerization

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89 Figure 3-2. Convergent method. Figure 3-3. Reaction of polymer chai ns with a difunctional monomer. Figure 3-4. Synthesis of a coupling agen t with 18 chlorosilane functions. + F F F *Multifunctional Coupling Agent Living polymer chains F = function *Living polymer chains+ R *+R R R R n R *R n Difunctional monomerCl3SiCH2CH2SiCl3+ MgBr 6 6 ClMgBr+ SiCH2CH2Si (I) (I)+6 HSiCl3 H2PtCl3(Cl3SiCH2CH2)3SiCH2Si(CH2CH2SiCl3)3

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90 Figure 3-6. Anionic synthesis of 4-ar m star branched polystyrene using 1,2bis(dichloromethylsilyl)ethane as functionalizing agent. Figure 3-7. Halogen-lithiu m exchange reaction. Figure 3-8. Synthesis of 4-arm star branched polymers using tetrabromomethylbenzene as linking agent. Figure 3-9. Synthesis of PI star polymer us ing HFPO as multifuncti onal coupling agent. C4H9 Si C2H4 Si OCH3 OCH3 OCH3 n 3Si B H3C B C2H4 Si B B CH3 PS 3PS PS PS 3 3 3Excessof PSb -oligoPBLi Benzene Met+RClx Cl +RMetClx-1 4 CH2Br BrH2C CH2Br BrH2C PMMALi PtBuMALi P2VPLi ++4 LiBr n-1 O F F CF3 F 1) 2) MeOH RT, 16h OH PI PI CF3 F n Li PILi

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91 Figure 3-10. Use of 1,3,5tris(1-phenylethenyl)ben zene as coupling agent. Figure 3-11. Use of fullerene C60 as linking agent for star polymer synthesis. Figure 3-12. Divergent method. 2 PS K +C60 THF 25 C 2 PS+C60 2 K 2 THF 25 C PSPS +C602 K 2 K +4 PS C602 K 2 THF 25 C X X X X +nM Multifunctional initiator Monomer Func t ional g r ou p s Specific functions depending on the polymerization typeF F F F C6H5 C6H5 C6H5 3 PS Li + CH2PS PSH2C C6H5 C6H5 CH2PS C6H5 Li Li Li

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92 Figure 3-13. Synthesis of three-ar med poly(propylene sulfide) star. Figure 3-14. Synthesis of four-arm PS star by the In-Out method. H N R O S HS N N O N O HS S NH R SH S H N R O O O H N R O S S N N O N O S S NH R S S H N R O O O S R' S R' S R' n n n1) DBU/DMF /-78 C 2)S 0C, 2h 3) R'X/NEt3RT, 1h R = R'X = Cl CH2 CH3 17or or CH3I 2 PS +Li PS PS Li Li PS PS PS Li Li PS

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93 Figure 3-15. Application of the I n-In method for star synthesis. Figure 3-16. Synthesis of dilithiated ( 1 ), trilithiated ( 2 ), and tetralithiated ( 3 ) initiators. Li 3+ Li Li Li THF 30 C Living PS chains Star polymer Double star polymer Br Br 2 s-BuLi Benzene Li Li Br Br Br 3 s-BuLi Benzene Li Li Li 1 1 2 2 H Br Br Br Br 3 4 s-BuLi Benzene H Li Li Li Li 3 + Br + Br + B r 2 3 44

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94 Figure 3-17. Scheme of the tetracarbani onic initiator/lithium 2-methoxyethoxide complex. Figure 3-18. Synthesis of four-armed polystyrene stars. H Br Br Br Br 3 2) s-BuLi Benzene H Li Li Li Li 3 HO OCH3 1)+O OCH3 Li 5 + 6 OH O H OH OH n n n n3 1) 2)O 3) CH3OH H Br Br Br Br 3 2) s-BuLi Benzene H Li Li Li Li 3 HO OCH3 1)+O OCH3 Li 5 +6 OH O H OH OH n n n n3 1) 2)O 3) CH3OH

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95 Figure 3-19. SEC eluograms of (PS)4 polystyrene and (PB)4 polybutadiene stars : a) protonated version of 3 ; b) polystyrene star; c) pol ybutadiene star; and d) flow marker.

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96 Figure 3-20. 1H NMR spectra (CD2Cl2 ; 400MHz) of (PB-OH)4 ( Mw,LS = 1800 g.mol-1; Mw/ Mn = 1.1) and (PB-OH)3 ( Mw,LS = 2400 g.mol-1; Mw/ Mn = 1.1) hydroxyl terminated star polymers.

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97 Figure 3-21. Reaction scheme for the synthesis of SBM star block terpolymers. Figure 3-22. SEC eluograms mon itoring the formation of a P(Sb -Bb -M)2 pentablock copolymer. (PSLi+)42) Styrene Benzene, RT, 12hP(Sb -BLi+)4P(Sb -BLi+)4Benzene, 5C to RT, 24h Benzene, RT, 1h 1) 2) CH3 O OMe, tert -Butylbenzene, -40 C, 1hP(Sb -Bb -MLi+)4 H O OMe p n m x y 4CH3OH H Li Li Li Li 1) 5

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98 Figure 3-23. SEC eluograms monito ring the formation of a P(Sb -Bb -M)n (n = 3 or 4) star block terpolymer: a) (PS)n polystyrene star; b) P(Sb -B)n star block copolymer; and c) P(Sb -Bb -M)n star block terpolymer.

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99 Figure 3-24. 1H NMR spectrum (CDCl3, 400 MHz) of P(Sb -Bb -M)3 star block terpolymer.

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100 Figure 3-25. Synthesis of (PBb -PEO)4 star block copolymers. CH OK OK n m KO n OK m O O H OH OH O H THF, RT n m m n (PB-OH)4 1) THF, 40 oC 2) H+, RT K + : Poly(ethylene oxide) block : Polybutadiene block : Polyphenylene core

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101 Figure 3-26. 1H NMR spectra (CDCl3 ; 400MHz) of a star copolymer (PB76b -PEO444)4 ( Mn,1H NMR = 94600 g.mol-1; Mw/ Mn = 1.22). Figure 3-27. SEC traces of the (PB-OH)4 precursor ( Mw,LS = 16 400 g.mol-1; Mw/ Mn = 1.05) and of the star copolymers (PB76b -PEOn)4 ( n = 57, 137, 444, and 1725) in THF.

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102 Figure 3-28. 1H NMR spectra (200MHz) of (PB76b -PEO444)4 in CD2Cl2 (A) and in CD3OD (B).

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103 Table 3-1. Characterization of PS and PB samples synthesized from 1 2 and 3 initiators, respectively. [a] Determined by SEC in THF using a multiangle laser light scattering detector. The d n /d c value was taken equal to that of linear polystyrene (d n /d c = 0.183cm3/g in THF). [b] Derived from refractometric detector. [c] n M(theo) = Mstyrene x ([Styrene]/[-PhLi]) x n ( n = 2, 3 or 4). [d] Average functionality of the samples as determined by 1H NMR. [e] Experimental values of : g=[ ]star/[ ]linear. [f] gR.W. = (2/f)1.5[0.396(f-1)+ 0.196]/0.586.215 [g] g= gR.W. 0.5 = [(3f-2)/f2]0.5.216 [h] g= K.F (K=2.37 and =-0.789).217 g(theo) n M[b] w M[a] w M / n M[b] n M(theo) [c] f [d] g[e] ZimmStockmayer[f]Berry[g] Grest[h] PS2 11000 11200 1.12 12000 1.9 80900 90800 1.08 89000 3.0 0.805 0.91 0.88 0.99 PS3 96700 131000 1.13 128000 3.0 0.846 0.91 0.88 0.99 31200 38400 1.08 39500 3.9 0.75 0.83 0.79 0.79 PS4 84700 98600 1.08 120000 3.9 0.79 0.83 0.79 0.79 PB3 25100 32500 1.03 30000 3.0 PB4 9400 16400 1.05 17200 3.9

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104 Table 3-2. Characterization of P(Sb -Bb -M)2 pentablock, P(Sb -Bb -M)3 and P(Sb -Bb M)4 star block terpolymer samples. PS P(Sb -B) P(Sb -Bb -M) w M[a] w M / n M[b] n M[c] w M / n M[b] n M[c] w M / n M[b] Microstructure (%1,2-(B))[d] (SBM)2 30000 1.09 350001.1 41000 1.2 60 (SBM)3 2800 1.08 5700 1.1 7500 1.1 75 (SBM)4 6100 1.05 121001.1 16100 1.2 70 [a] Determined by SEC in THF using a multiangle laser light scattering detector. The d n /d c values of PS was 0.183 cm3/g in THF. [b] Derived from refractometric detector. [c] Determined by 1H NMR from the molar mass of th e polystyrene block, assuming 100% efficiency in the initiation of the second and third blocks. [d] Calculated by 1H NMR.

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105 Table 3-3. Characteristics of hydroxyl functionalized (PB-OH)n star polymers and (PBb -PEO)n (n = 3 or 4) amphiphilic star block copolymers. a) Determined by SEC in THF equipped with a mu ltiangle light scatteri ng detector. The d n /d c value was measured in THF (d n /d c = 0.094 cm3/g). b) Apparent molar masses determined by SEC in THF using a polystyrene calibration. c) Mn,th = MButadiene x ([Butadiene]/[-PhLi]) x n (n = 3 or 4). d) Estimated by 1H NMR analysis. e) Mn,th = MEO x ([EO]/[(PB-OH)4] + Mw,(PB-OH)n (PB-OH) star precursors Amphiphilic (PBb -PEO) star copolymers Stars Mw a) Mw/ Mn b) Mn d) Mn,th c)%1,2PBd) Mn a) Mn,est d) Mn,th e) Mw/ Mn a)Code 45900 42500 40500 1.2 (PB200b -PEO76)3 56000 75500 77500 1.15 (PB200b -PEO326)3 58000 160500 164500 1.2 (PB200b -PEO970)3 (PB-OH)3 32500 1.03 31000 3300076 74000 320500 323000 1.2 (PB200b -PEO2182)3 28300 26200 27000 1.23 (PB76b -PEO57)4 29400 40600 41500 1.32 (PB76b -PEO137)4 34500 94600 96000 1.22 (PB76b -PEO444)4 (PB-OH)4 16400 1.05 15000 1700064 45800 320000 318000 1.19 (PB76b -PEO1725)4

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106 CHAPTER 4 TWO-DIMENSIONAL POLYMERIC NANOMA TERIALS THROUGH CROSS-LINKING OF POLYBUTADIENEB -POLY(ETHYLENE OXIDE) MONOL AYERS AT THE AIR/WATER INTERFACE 4.1 Introduction and Literature Overview The idea of stabilizing amphiphile self-asse mblies by polymerization was introduced at least 30 years ago for monolayers and about 10 years later for bilayer vesicles.226,227 This emerging approach to bridging the nanoscale world of labile, interfacially driven self-assemblies with the meso-scale has resulted in several ex amples of massively cros s-linked 3D structures.228232 For example, Bates and colleagues228 were the first to succeed in retaining the cylindrical morphology formed by gigantic wormlike rubber micelles of polybutadieneb -poly(ethylene oxide) PBb -PEO diblock copolymers in water by chemi cal cross-linking of the PB cores through the pendant double bond of the 1,2-polybutadiene units (Figure 4-1) using water-soluble redox combination of potassium persulfate (K2S2O8) and sodium metabisulfite (Na2S2O5)-ferrous sulfate (FeSO4. 7H20) for the initiation of cross-linking. This type of free-radi cal initiat or, used extensively in emulsion polymerizations,233 is ideally suited for generating a specified number of radicals in the aqueous phase th at are subsquently captured by the nanoscopic micelles. In this work, the authors produced a relatively high c oncentration of radicals, one for every two PB double bonds, thereby ensuring a high degree of cross-linking without disruption of the cylindrical morphology. Although they have not dete rmined the exact cross-link density for the chemically fixed micelles, experiments indicate that every block copolyme r has been covalently bonded together within individual giant wormlik e molecules. For exam ple, extraction with chloroform, which efficiently removes unreacted block copolymers from aqueous solution, fails to recover any detectable PBb -PEO linear diblock copolymers from the cross-linked system.

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107 The Bates group232,234 also proposed the fabrication of massively cross-linked and property-tunable membranes by free-radical polym erization of self-assembled, block copolymer vesiclespolymersomes (Figure 4-2). They described a PBb -PEO diblock copolymer that has a hydrophilic weight fraction like that of lipids and forms robus t fluid phase membranes in water. The polymersomes sustain free radical polyme rization of the hydrophobi c butadiene, thereby generating a semipermeable nano-shell. Cross-linked giant vesicles proved stable in chloroform and could also be dehydrated and re-hydrated without modifyi ng the ~9 nm thick membrane core; the results imply defectfree me mbranes many microns-squared in area. However, relatively few groups have shown in terest in stabilizati on by cross-linking of two-dimensional (2D) copolymer self-assemblies fo rmed at the air/water interface; most studies have involved interfacial polymerization of small molecules in Langmuir monolayers.235-263 In the early 1970s the group of Veyssi235,237,240,241 was the first to demonstrate the formation of 2D cross-linked material by cr oss-linked polymerization of monolayers of dimethacrylates, and several other difunctiona l reactive amphiphiles under UV irradiation at a constant surface pressure at the air/water or oil/wat er interface. This idea was further followed by other groups. Regen and colleagues238,239 introduced the concept of a 2D-network of molecular pores, i.e., perforated monol ayers derived from calix[ n ]arene-based amphi philes. For this purpose, they employed a series of derived calix[ n ]arene-based amphiphilic surfactants (mercurated calix[ n ]arene,238,239 thio-, amide-, thioamideor imine-functionalized calix[ n ]arene,244-246 or unsaturated calix[ n ]arene245) to form stable monolayer at the air/water interface (Figure 4-3). By pol ymerization of the calix[ n ]arene-based molecules either by introduction of a cross-linking agent such as ma lonic acid (Figure 4-3B ) or via UV irradiation, they were able to synthesize porous and cohesive perforated monolayers (pore diameters in the

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108 range 2-6 ) that can function as molecular sieves for gas pe rmeation selectivity (Figure 43A).245,246 The Michl group252,259 proposed the prepara tion of 2D grids through 2D supramolecular chemistry. The general strategy consists in the linear coupli ng of arm-ends of star-shaped monomers forced to adhere to a surface (mercury surface in this case) with their arms parallel to the surface. After the polymerization of the st ar-shaped monomer (for example, the anionic lanthanum sandwich complex of tetrapyridylporphyrin, Figure 4-4b) by introduction of a coupling agent ( p -xylylene dibromide, Figure 4-4a) by di ffusion from a solution contacting the surface, well-defined covalent 2D squareor hexagonal-grid polymers could be synthesized (Figure 4-4c and d).252,259,264 They also proposed the preparat ion of 2D grids through cationbonded or hydrogen-bonded supramolecular chemistry.265-267 Palacin and colleagues242,243,247 also designed supermolecular assemblies of amphiphilic porphyrins by molecular engineering through mo lecular recognition between oppositely charged monomers at the air/water inte rface. Two porphyrin monomers P2 and P3 bear four positive charges while the thir d porphyrin monomer P1 bears four ionizable ca rboxylic functions (Figure 4-5): via an acid/base reacti on between the funtional groups of each macrocycle, spatially oriented flat-lying heterodimers P1-P2 and P1-P3 are spontaneously formed at the air/water interface. Kloeppner and Duran254 were the first to demonstrate mechanical properties sufficient to allow the removal of free standing fibers from the water surface a 2D cross-linked 1,22-bis(2aminophenyl)docosane (BAD) polyanilines. For th is purpose, the oxidative polymerization of BAD at the air/aqueous interface was done in the presence of a strong chemical oxidant, ammonium peroxydisulfate, and an acid (sulfu ric acid). The polymerization was monitored by observing the barrier movement need ed to maintain a specific a pplied surface pressure, assuming

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109 that the polymerization rate can be calculated from the change in the area of the surfactant at a constant surface pressure. OBrien and colleagues226 described three different appr oaches (thermal with AIBN, redox with potassium persulfate or sodium bisu lfite, or photoirradiation polymerizations) to polymerize monomeric lipids in a two-dimensional assembly pr oceeding in a linear or crosslinking manner depending on the number of polymerizable groups (double bonds) per monomeric lipid. Lipids that contain a single reactive moiety in either of the hydrophobic tails or associated with the hydrophilic head group yield linear poly mers. Polymerization of lipids with reactive groups in each hydrophobic tail generally yield cross-linked polymeric networks. Teyssi and colleagues260,262 proposed the first spontaneous styrene sulfonate polymerization in Langmuir films following an anionic mechanism. Indeed, when a dioctadecyldimethylammonium bromide (DODA) monolayer is spread over styrene sulfonate (SSt) aqueous solution, this monomer was sh own to undergo a spontaneous polymerization process. This process was followed by monitoring the surface pressure variations at constant molecular area and/or the molecular area variation at constant surface pressure versus time. The spontaneous polymerization characteristics depe nd upon the monomer concen tration, the surface pressure, the subphase ionic streng th and pH. The polymerization occu ring at the interface with a probable anionic mechanism is inhibited by ca rbone dioxide, sodium bicarbonate and LiClO4. Finally, Carino et al.257,258,263 followed the 2D gelation during the polymerization of alkylalkoxysilane molecules under acidic conditions at the air/water interface by monitoring the mean molecular area decrease and the surface visc osity increase versus time as the monolayer was cross-linked. They also used brewster angle microscopy to show the complete coverage of the water surface by the cross-linked material at the end of the reaction (Figure 4-6).

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110 Concerning the cross-linking between true amphiphilic copolymeric chains at the air/water interface, only one example based on a polymerizable lipopolymer was previously proposed by OBrien and colleagues.268 The amphiphilic copolymer investigated had a linear hydrophilic backbone consisti ng of poly(ethylene imineco -ethyl oxazoline) and containing 20 % of hydrophobic sorbyl side chains making it capable of formi ng stable Langmuir monolayers (Figure 4-7). Network formation after photopolyme rization of the sorbyl moiety upon UV light exposure was demonstrated by monitoring the surface dynamic shear modulus (elasticity measurement). Unfortunately, they were not able to characterize the 2D morphologies obtained before and after the cross-linking reaction. 4.2 Interfacial Behavior of (PBb -PEO)n (n = 3 or 4) Star Block Copolymers at the Air/Water Interface Amphiphilic block copolymers containi ng both hydrophilic and hydrophobic segments form an important class of mate rials due to their wide variety of potential applications as polysoaps, polymeric surfactants, solution modifiers, emulsifiers, wetting agents, foam stabilizers and drug carriers.269-271 In most of the above areas, controlling the size as well as the surface properties of block copolymer assemblies is a major issue. In this chapter, we investigate star copolymers containing poly(butadiene) (PB) blocks. The amphiphilic character of block copolymers has also been widely exploited for the preparation of monolayers at th e air/water interface. These monol ayers are somewhat different from classical low molecular weight amphiphile s in that the copolymer is constituted of hydrophilic and hydrophobic blocks of considerable molecular weight. The hydrophilic block by itself would be soluble in water, but the hydro phobic block acts as a bu oy, anchors the polymer chains at the interface, and thus prevents the hyd rophilic part from dispersing into the bulk water subphase. Numerous studies published on the field of monolayers at the ai r/water interface during

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111 the past years demonstrate the utility in using the nonelectro lyte poly(ethylene oxide) (PEO) water soluble block due in particular to its pr operties and its biocompa tibility and subsequent potential for applications in drug-delivery and other fields. Among copolymers investigated at the air/water interface, polystyreneblock -poly(ethylene oxide) (PSb -PEO) block copolymers certainly form the most commonly studied systems.272-290 Although PS is a convenient choice due to it s inexpensive price, monomer availability, and facile synthesis, polybutadieneb -poly(ethylene oxide) (PBb -PEO) is the primary amphiphilic diblock copolymer studied to provide control over spherical rodlike and vesicular architectures in bulk or aqueous solutions.228,234,291,292 Furthermore polybutadiene offers the possibility to stabilize block copolymer a ssemblies by cross-linking through the pendant double bond of the 1,2-polybutadiene units. However, in spite of the significant interest showed for PBb -PEO copolymers, few groups have studied the behavior of such amphi phiplic copolymers at the air/water interface.293295 Among these, only Discher and colleagues293 were able to show characteristic morphological organization of this amphiphile at the air/water interf ace through AFM images, and were the only ones who attempted crosslinking stabilizati on. Moreover, the behavior of any PBb -PEO diblock copolymer with architecture more complex than linear chains, whether in bulk, in solution, or at the interface has not ye t been investigated. The structure of the AB diblock copolymers either in the bulk state or in solution is most certainly influenced by the volume fraction of ea ch block and by the segment-segment interaction parameter but the molecular architecture, the conf ormational asymmetry and the compositional fluctuations all also have an effect on structure.296 Systematic investigation of the influence of all these factors on the organization of AB diblock copolymers in a st ar architecture necessitates the

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112 preparation of monodispersed materials with well-defined molecular weights, block volume fractions and architecture.297 4.2.1 Surface Pressure-Area Isotherms Surface property characterizati on of the four different (PBb -PEO)4 star block copolymers started with isotherm measurements. Fi gure 4-8 shows the surface pressure-area ( -A) isotherms (25C) on compression with a log scale on the x-axis for convenien t visualization. The isotherm of each copolymer was reproducible and indepe ndent of spreading solution concentration. Together, the isotherms revealed several characteristics. First, all the monolayers were compressible up to surface pressures beyond 30 mN.m-1. Second, all of the isotherms are characterized by the three distinct regions illust rated in the cartoons of Figure 4-8: at high molecular areas the so-called pancake region (I), a pseudoplateau (II), and the brush region (III) at low surface areas. The dot ted lines in Figure 4-9 also shows the extrapolation used to estimate the three corresponding parameters Apancake, Ao, and A. Third, the pressure of the pseudoplateau region was very similar for all sample s, while its width vari ed systematically. In fact at the highest PEO com position, the pseudoplateau represents more than a 50-fold compression. Fourth, the copolymers (constituted from the same PB core and different PEO chain lengths) occupied similar areas in the high pressure brush regi on, independent of the PEO chain length. Considering the affinity of PEO for the ai r/water interface and th e hydrophobicity of PB, we suppose that the expanded surface film at la rge molecular areas (I) corresponds to a film dominated by the behavior of PEO at the surface. Quantitative comparison of Apancake, the area occupied by the pancake-like PEO domains when adsorbed at the air/water interface, supports this interpretation. A fit of the data revealed a linear dependence of Apancake with the number of

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113 EO units (y = 1.399x + 113.09; R2 = 0.989) indicating that the pan cake region area was largely dependent on the PEO block length (Figure 4-10). Second, as the monolayer is compressed, a ps eudoplateau is observed at a pressure of about 10 mN.m-1, which is a signature of adsorbed EO monomer units at the air-water interface.298,299 The length of the PEO block clearly in fluences the length of the pseudoplateau ( A) as seen in Figure 4-11. In fact, a fit of A with the number of EO units gives the very good linear dependence (y = 0.6136x-6.0107; R2 = 0.999) shown by Figure 4-11. The magnitude of the slope, 61 2/EO repeat unit, is reasonable for EO units lying flat at the interface. The observed linearity and small intercept implies that the change in area between Apancake and Ao can be interpreted by PEO segments being successive ly submerged into the water subphase during compression at approximately 10 mN/m along the pseudoplateau. This is also in qualitative agreement with previous studies on analogous PSb -PEO star block copolymers at the air/water interface.282,283 Upon further compression, a second large pressure increase is observed up to values of 32 mN.m-1, a trend also observed in the case of PBb -PEO linear block copolymers.293,294 In this regime of high density, a brush conformation is expected. The latter is supported by the theoretical area A0 that a compact film would occupy at ze ro pressure. Table 41 reveals that the occupied surface area A0 is effectively the same for all the four samples (A0/molecule = 32 4 nm2). The low area per butadiene repeat unit is a strong indication that th e PB units have been compressed into a 3D structure rather than lying fl at at the air/water interface. This result also confirms that only the PB segments have an effect on the brush regi on since the copolymers synthesized all possess the same PB core size.

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114 4.2.2 Film Relaxation By hysteresis experiments, we then inves tigated the ability of these four arm (PBb -PEO)4 stars to relax to the same area as that occupied in their orig inal uncompressed state. We examined the effects of pressure varia tion, compression/expansion cycles and the PEO block length on the degree of hysteresis and these results are shown in Figure 4-12. Pressure variation. As shown in Figure 4-12 A, at low pressures ( mNm-1), only minimal hysteresis was observed on compression a nd expansion, indicating that the surface films were capable of expanding at the same rate as they were compressed independent of the PEO block length. Thus, the star copolymers are elastic and highly surface active in the low pressure region I. For pressures in the range of 10 mN.m-1 a dramatic increase in hysteresis was observed with increasing pressure as shown in Figure 4-12B and C. This trend is consistent with the interpretation that a hi gher surface pressure ( 10 mN.m-1) is necessary to start to submerge the higher molecular weight PEO branches into the water subphase. The observed compression/expansion curves also indicate that the surface film now relaxes at a slower rate than the compression. Compression/expansion cycles. Hysteresis also changed with repeated compression/expansion cycles. At lower pressures ( < 8 mN.m-1), the hysteresis remained relatively minor and independent of the number of compression-expansion cycles applied. In contrast, at higher pressures, the degree of hysteresis, the wi dth of the pseudoplateau, and the pancake limiting area systematically changed. The large initial hysteresis in Figure 4-12B-left may indicate reorganization of the high molecular weight PEO arms between the first and second compression. Subsequent creep to smaller surface areas indicate that with each cycle, slightly

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115 more PEO is submerged into the water subph ase and does not resurface over the time of the experiment. However, we obs erved at higher pressures ( > 10 mN.m-1) that for samples consisting of very long PEO chains ((PB76b -PEO1725)4 ; Figure 4-12C-left), the compression curve of one cycle does not match the expansion curve of the previous cycle, but match the compression curve of the previous cycle, unlike short PEO sample. In this last case, it could be supposed that because of the very long PEO blocks, it is very difficult to submerge all EO units into the water subphase and some could resurf ace at the air/water interface upon expansion. 4.2.3 AFM Characterization of the Transferred Monolayers Atomic Force Microscopy was used to study the morphology of surface films at the air/water interface after tr ansfer to a solid surface. To this end, Langmuir-Blodgett films of two different samples (PB76b -PEO1725)4 and (PB76b -PEO57)4 were transferred to mica substrates over a range of pressures. Table 4-2 and Figur e 4-13 shows that for applied surface pressures below 9 mN/m, positive transfer ratio values of approximately 1.0 were observed indicating ideal transfer with no change in macroscopi c film dimensions. Whereas surface pressures above 8 mN/m lead to transfer ratios of appr oximately 2.0, or significan t densification of the surface film upon transfer. In all cas es LB transfers were character ized by a linear instantaneous transfer ratio indicating that the monolayer was transferred uniformly over the entire mica substrate. Due to the hydrophilic nature of the mica, we assume PEO transfers as the bottom layer, represented in the scanned images as the contin uous dark phase, wherea s PB occupies the top portion of the film corresponding to the white higher elevation mi crodomains shown in Figure 414.

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116 Effect of surface pressure. First, an effect of the surface pressure can be seen (Figure 414) in the pancake region for the sample with the longest PEO blocks. At lower pressures ( = 2 mN.m-1) the PB microdomains are not homogeneous in size. However, when increasing pressure from = 2 mN.m-1 to 8 mN.m-1 the PB microdomains are more organized, of larger size and less numerous for a same area. These ob servations were confir med by the quantitative analysis of the AFM scans shown in Table 43. In comparing AFM scans (Figure 4-14A D), first a gradual increase in the diameter of PB domains (from 61 to 132 nm), their height (from 2 to 5 nm), and in the number of molecules per PB domain (from 4 to 186), and second a decrease in the number of PB domains (from 445 to 18) a nd in the PB coverage (from 32% to 6%) with the surface pressure increasing were observed (Table 4-3). The above trend is also observed in the mol ecules/domain vs. pressure curve of Figure 415, which shows more molecules continually a ggregating (dramatic increase above pressure = 4 mN/m) to form larger circular 2D micelles. This data is a strong in dication that the surface micelles formed on spreading the PBb -PEO stars are fluid and dynami c at the air/wa ter interface in sharp contrast to PSb -PEO systems where vitrification of PS leads to frozen surface micelles. The AFM data also show that during co mpression, the distance between the PB microdomains increases from an average distance of 70 nm at = 2mN.m-1 to 540 nm at = 8mN.m-1. The estimated theoretical length of one extended PEO branch (1725 EO units and assuming 3.19 per EO unit) is about 550 nm, which is very close to the average distance between two PB microdomains at = 8 mN.m-1 (540 nm) illustrated in Figure 4-16. At higher pressures ( > 8 mN.m-1), a second type of morphology is observed (Figure 414E H). This change in morphology is mirrored by a significant increase of the transfer ratio (T.R.) illustrated in Figure 4-13. The sudden jump in T.R. from 1.0 to 2.0 implies significant

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117 densification of the f ilm upon transfer in the pseudoplateau region ( 8 mN.m-1). The AFM data show that at = 9 mN/m, PB microdomains are spa ced much more closely compare to = 8 mN/m and then form elongate d stripes, or chains, at = 10 mN/m. The onset of the chain morphology correlates with the onset of significan t hysteresis (Figure 412C) observed with the PEO1725 blocks. Moreover, neither the chain mor phology (Figure 4-14I and J) nor the same hysteresis (Figure 4-12C) is observed for the shorter PEO57 material, indicating a PEO length influence chaining aggregation. The observed results led to the model shown in Figure 4-16 for the (PB76b -PEO1725)4 block copolymer. At low pressure, microdomains of polydisperse size, some 2 nm vertical thickness, and few polymer chains per domain ar e observed. The relatively low density of PEO chains allows these domains to be closely spa ced and the PEO chains to be in a relatively compact conformation. Upon compre ssion the PB domains clearly flow and coalesce to form progressively larger surface micelles of more monodisperse size and higher and higher PEO chain densities that should lead to an overall extension of the PEO segments. We suppose that reduction in the line tension between the PB and PEO rich phases helps dr ive the aggregation. This process also increases the vertical thickne ss and significantly increases the lateral spacing between domains. At hi gher surface pressure ( > 8 mN.m-1), and perhaps also associated with compaction during LB transfer, we suppose the PB microdomains start to chain as illustrated in Figure 4-16C. During chaining we hypothesize that the long PEO chai ns are further extended in a direction perpendicular to the chain axis and this hinders s pherical aggregation and favors aggregate through points of contact at opposite e nds of the elongated domain. Similar surface morphology has also been observed in the case of PBb -PEO linear block copolymers.293 At

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118 higher applied surface pressures, we suppose that the remaining PEO chains are hydrated and larger aggregates are formed, quick ly leading to thicker films. In contrast, we suppose that the short PEO branches of the (PB76b -PEO57)4 material are much more easily submerged into the water subphase at higher pressure, and micelle chaining is hindered. 4.3 Cross-linking of Polybutadieneb -Poly(ethylene oxide) Monolayers at the Air/Water Interface We are interested in crosslinking monolayers of block c opolymers to achiev e porosity at the submicron scale. Here, a 2D polymeric na nomaterial consisting of a continuously crosslinked polybutadiene material wi th poly(ethylene oxide) domains of controlled size trapped within the PB network is illustrated. The strategy opens up the possibility to retain a specific morphology at the mesoscopic scale defi ned by a given surface pressure ( ). Such porous polymer thin films have potential applications in the preparation of membranes which will show large differences in permeability to water, methanol, and other polar compounds depending on the effective PEO pore size. With this in mind, we inves tigated two different methods for forming 2D cross-linked monolayers with a (PBb -PEO)3 amphiphilic star block copolymer material based on a polybutadiene core and a poly(ethylene oxide) co rona. In the first method, cross-linking of the PB hydrophobic block was achieved by using AIBN as a radical init iator under UV light directly at the air/water interface. The second method was based on the self-condensation of the triethoxysilane-functionalized polybutadiene blocks of the (PB(Si(OEt)3)b -PEO)3 star block copolymer under acidic conditions. Th e latter route is extremely general and should be applicable to functionalization and coupling via other silanes and metal alkoxides. In both cases, the surface properties of the cross-linked ma terials were characterized by su rface pressure measurements

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119 such as surface pressure-mean molecular area ( MMA: interfacial area occupied by one polymer molecule) isotherms at different reaction times and isobar experiments (MMA evolution versus time for a given at different subphase pH values. Th e monolayer morphologies obtained at different surface pressures were studied by atomic force microscopy (AFM) imaging the Langmuir-Blodgett (LB) films obtaine d before and after cross-linking. 4.3.1 Interfacial Behavior of (PBb -PEO)3 Star Block Copolymers We first investigated the surface properties of monolayers of a new set of (PBb -PEO)3 amphiphilic three-arm star bloc k copolymers at the air/water interface. A divergent anionic polymerization method yielded copolymers with well-defined architecture, molecular weights, and block volume fractions (Chapter 3). Different sa mples of well-defined (PBb -PEO)3 amphiphilic star block copolymers exhibiting na rrow molecular weight distributions were prepared with poly(ethylene oxide) coronas over a broad range of volume fractions (Table 4-4). Isotherm experiments at the air/water interfac e showed three characteristic regions: a pancake region (I) at high mean molecular areas where slowly increases as the monolayer is compressed, a pseudoplateau at a pressure of ca 10 mN/m (II) that corresponds to the dissolution of the PEO chains and finally a compact brush region (III) at low surface areas affected only by the PB segments (Figure 4-17). A fit of the ps eudoplateau data revealed a linear dependence of A with the number of EO units (y = 12.351x 0,4889; R2 = 0.99) indicating that the pseudoplateau region area was largely dependen t on the PEO block length (Figure 4-18). The extrapolated curve falls almost perfectly through the or igin with a x-axis intercept co rresponding to less than 1 EO unit, indicat ing a strong phase separa tion between blocks compared with slight intermixing observed with PS-PEO systems. Our data indicate that along the pseudoplateau, a

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120 monomer of EO occupies 12.4 2, which is in good agreement with the value found for PS-PEO systems.282,283 The monolayers were also transferred as Langmuir-Blodgett film s on mica at various surface pressures and analyzed by Atomic For ce Microscopy (AFM) (Figure 4-21A), showing different morphologies from analogous (PSb -PEO) star copolymers.282,283 4.3.2 Reaction of the Polybutadiene Block at the Air/Water Interface in the Presence of AIBN Initially, photocleavage of AIBN under UV light was attempted to crosslink the hydrophobic PB blocks of the (PBb -PEO)3 copolymer monolayers directly at the air/water interface. For this purpose, 100 L of a solution of (PB200b -PEO76)3 star block copolymer in chloroform at a concentration of C = 1 mg/mL and 100 L of a solution of AIBN in chloroform at a concentration of C = 0.2 mg/mL were successively deposited on the water surface. The monolayer was then compressed up to the desire d surface pressure (20 mN/m) and the radical polymerization reaction of the 1,2-PB do uble bonds initiated by the photo-induced dimethylcyano radicals was carri ed out for 24 hours. At the e nd of the reaction, the surface properties of the reacted material were inves tigated through isotherm and AFM studies. As shown in Figure 4-19, a shift towards the low m ean molecular area regi on was observed after reacting the polybutadiene blocks. Furthermore, the progression of the reaction was followed by IR analysis of an aliquot of the material rem oved directly from the water surface (Figure 4-20). The disappearance of the peaks at 3100 cm-1 and 1600 cm-1 corresponding to the 1,2-PB double bonds (=CH2 anti-symmetric stretch and alkenyl HC=CH2 stretch, respectively) confirmed significant consumption of the pendant double bonds. AFM characterization of the morphologies obtained before and after the reaction confirmed the previous observations. Figure 4-21 shows images of monol ayers transferred to

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121 mica substrates at = 20 mN/m at different reaction times. The images reveal submicron-sized white circular domains that enlarge with reac tion time, but remain separated. Due to the hydrophilic nature of mica, we a ssume PEO transfers as the bottom layer, represented in the images as the continuous dark phase, wherea s PB occupies the top portion of the film corresponding to the white higher elevation domains shown in Figure 4-21A. We suppose that the bright domains correspond to crosslinked PB re gions. The fraction of the surface occupied by the bright domains increases with the reaction time until large portions of the surface is covered with cross-linked and hydrophobic PB after 24 hours. However, the picture scanned at 40 m (Figure 4-21E) reveals that the bright domains remain isolated from each other and do not interconnect across the film. The formation of these domains is consistent with a chain polymerization occurring precisely at the spots of a radical initiation, which ar e also the nucleation spots. The continuous PEO phase indicates that while some areas might have reacted, this st rategy failed to afford homogeneously cross-linked PB covering the entire surface. 4.3.3 Cross-linking with Hydrosilylated Polybuta diene Blocks at the Air/Water Interface 4.3.3.1 Application on polybutadiene homopolymer To successfully demonstrate the viability of our method, we utilized linear polybutadiene which is commercially available because of its world wild application as a commodity rubber (Figure 4-22). Unsaturated polymers, especially diene polymers, are ideal for selective chemical modification because of the technological importan ce associated with the parent materials. A particularly interesting reaction involves the hydrosilylation of diene polymers to obtain silanemodified rubber materials. Many papers and pate nts have appeared on the hydrosilylation of polymers.300-312 In most cases, the hydrosilylated polydien es were used for the synthesis of macromolecular complex architectures such as arborescent graft polybutadienes,313 multigraft copolymers of polybutadiene and polystyrene,314 or side-loop polybutadiene.315

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122 We apply here the hydrosilylation reaction on the double bonds of polybutadiene chain polymers. Triethoxysilane was used as the hydros ilylating agent in stoichiometric amount with the total molar amount of double bonds in the polybutadiene chain (1,2and 1,4-units), and platinum(0)-divinyltetramethyldisiloxane complex (Karstedt catalyst) was used as the catalyst (Figure 4-22). The reaction was he ated up under argon for 24 hours at 80 C in dry toluene (water free environment). After workup, the hydros ilylated copolymer was analyzed by 1H NMR and FTIR spectroscopy (Figures 4-23, 4-24, and 4-25). The 1H NMR spectrum of the polybutadiene starti ng material was used to determine the distribution of 1,2and 1,4-units. The two protons of the pe ndant vinyl carbon in the 1,2-units (=C H2) and the other hydrogens in the double bonds (-C H =C H and C H =CH2) having chemical shifts of 4.9 ppm and 5.4 ppm, respectively, the pol ybutadiene turned out to be composed of 89 mole % of 1,2-PB units (Figure 4-23). The 1H NMR spectrum of the hydrosilylated polybutadiene revealed a strong d ecrease in the intensity of th e signal corresponding to the CH=C H2 ( = 4.9 ppm) protons of the pendant double bon ds. Furthermore, the appearance of intense peaks at = 1.2 ppm and = 3.8 ppm corresponding resp ectively to the SiOCH2C H3 methyl protons and SiOC H2CH3 methylene protons indicated a high degree of conversion. However, some pendant double bonds remained unreacted after hydrosilylation (Figure 4-24). Based on the integration values of the signals at = 4.9 ppm and = 5.4 ppm, a conversion of 75 % of the 1,2-PB pendant double bonds was f ound, knowing that trie thoxysilane reacts predominantly with the 1,2-PB un its as previously demonstrated.312 This result was confirmed by IR spectroscopy as shown in Figure 4-25, where the absorbance peaks at 3100 cm-1 and 1640 cm-1 characteristic of CH=CH2 double bonds (=CH2 anti-symmetric stretc h and alkenyl HC=CH2 stretch, respectively) strongly decreased in

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123 intensity after hydrosilylation. However, there are still unreacted pendant double bonds remaining after reaction indi cating less than 100% conversion. After characterization of the PB68co -PB(Si(OEt)3)136 triethoxysilane -functionalized polybutadiene, its cross-linking at the air/ water interface by self-condensation of the triethoxysilane pendant groups was studied. Alkylalkoxysilanes have been widely used as reactive amphiphilic molecules at the air/water interface.257,258,263,316-327 Our group has for instance in vestigated some of the fundamental aspects of the chemical cross-li nking of octadecyltrimethoxysilane (OTMS) and octadecyltriethoxysilane (OTES) molecules unde r acidic conditions at the air/water interface.257,258,263,327 The mechanism of this 2D-acid-catalyzed cross-linking involves two different steps (Figure 4-26): first, the hydrolys is of the ethoxy groups with th e elimination of three ethanol molecules to give the corres ponding silanols, followed by conde nsation between the silanols leading to the formation of a 2D-network. The air/water interfacial cross-linking of the chemically modified PB(Si(OEt)3) polybutadiene was first studied by recordi ng isotherms after different reaction times (subphase pH = 3.0 and = 0 mN/m) (Figure 4-27) with a barrier compression speed (100 mm/min) to prevent additional cross-linking during monolayer compression. For comparison, the blue curve illustrates the same polymer spread and rapidl y compressed at pH = 3.0 before any significant reaction could occur (Figure 4-27). As the reaction time is increased, the isotherms shift towards the low mean molecular area region (loss of et hanol and water molecules during hydrolysis and condensation, respectively). For reaction times longer than 10 hour s, the isotherms essentially overlapped which indicates comp letion of the cross-linking.

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124 As shown in Figure 4-28 the monolayer static elastic modulus s calculated from the expression (1):328 dMMA d MMA s (1) significantly increases versus reaction time, indicating that the ma terial becomes more and more rigid as the extent of cross-linking is increased. From these isotherms, the interfacial area occupied by one silane repeat unit before reaction and its decrease during cr oss-linking were estimated ( = 5 mN/m, pH = 3.0) and compared with the values previously reported for OTES under similar experimental conditions.327 The MMA for the hydrosilylated pol ybutadiene decreases from 6300 2 (46 2/silane repeat unit) down to 3520 2 (26 2/silane repeat unit), wh ich corresponds to a decr ease of approximately A = 20 2/silane repeat unit. These values are in ve ry good agreement with the ones reported for OTES (46 2/molecule before cross-linking, 24 2/molecule after cross-linking, and A = 22 2/molecule), and they clearly i ndicate that the extent of solgel cross-linking is not reduced when starting from true polymeric chains compared to alkylalkoxysilane molecules. The pH influence on the cross-linking reacti on kinetics was shown by carrying out isobar experiments at = 10 mN/m and for different subphase pH values (Figure 4-29). As expected, the MMA decreases faster for lower pH values. Th e isobar at pH = 7.0 shows a very slow creep over time which demonstrates that the reaction is likely insignificant unde r neutral pH conditions. For lower pH values (pH = 2.0 and 3.0), the cu rves overlap with the MMA leveling off after about 7 hours indicating completion of the crosslinking reaction. The kine tics were consistent with those reported for OTES and were slow er compared to the results obtained for

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125 OTMS,257,258,263,327 which is related to the slower elimina tion of larger alkoxy substituents during the hydrolysis step. Upon completion of the crosslinking reaction, the cross-linked material could be subsequently manually removed from the interface with a spatula after its compression to a final area of ca. 2 x 15 cm2 (Figure 4-30), leading to a film of approximately 50 monolayers thick. It was self-supporting and gel-like, and could be colle cted as elongated sheets, which in turn could be drawn into very long fibers at high elongation (Figure 4-30). As expected, it was insoluble in common organic solvents such as chloroform or THF, making molecular weight analysis by SEC impossible. The evolution of the monolayer morphology during cross-linking was characterized by AFM imaging of the LB film after tran sfer onto mica substrates (Figure 4-31, = 10 mN/m). As a control experiment, it was firs t observed that under neutral pH conditions (pH = 7.0, no crosslinking) the hydrosilylated polybutad iene forms a smooth and feat ureless monolayer (Figure 431B) in opposition to the highly hydrophobic polybutadie ne starting material which forms typical rubbery continuous aggregates above the water su rface (Figure 4-31A). Afte r its hydrosilylation, the polybutadiene becomes amphiphilic (hydro phobic backbone and hydrophilic triethoxysilane side groups) and consequently surface active with the triethoxysilane penda nt groups solvated into the water subphase. This interfacial prope rty of the hydrosilylated polybutadiene was also shown in the isotherms where stab le monolayers could be formed for surface pressures as high as 40 mN/m before collapsing (Figure 427). After 20 minutes of reaction ( 50 % extent of crosslinking according to the isobar at pH = 3.0 and = 10 mN/m), the cross-linked material becomes more hydrophobic and can be clearl y observed in Figure 4-31C (bri ght areas) with an average height of 1 nm as determined by cross-sect ion analysis (Figure 431E). The cross-linked

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126 polybutadiene has irregular borders and doesnt c over yet the entire mica surface. An AFM image obtained after completion of the cross-linking reaction is shown in Figure 4-31D (10 hours, pH = 3.0, = 10 mN/m). Under these experimental cond itions, most of the mica surface was covered with a smooth and cross-linked monolayer. Theref ore, we deliberately fo und an area with a crack (that probably formed during film transfer) to clearly show th e presence of the cross-linked monolayer (bright area) on top of the mica substrate with a thic kness that stays constant around 1 nm during cross-linki ng (Figure 4-31F). 4.3.3.2 Application on (PBb -PEO)3 star block copolymer Hydrosilylation of (PBb -PEO)3 star block copolymers. We also applied the hydrosilylation reaction on the polybutadiene segments of the (PB200-b-PEO326)3 star block copolymer. Triethoxysilane was used as the hydro silylating agent in stoi chiometric amount with the total molar amount of double bonds in the pol ybutadiene block (1,2 and 1,4 units), and platinum(0)-divinyltetramethyldisiloxane complex (Karstedt catalyst) was used as the catalyst (Figure 4-32). The reaction was he ated up under argon for 24 hours at 80 C in dry toluene (water free environment). After workup, the hydr osilylated copolymer was analyzed by 1H NMR and FTIR spectroscopy (Figures 4-33 and 4-34). Figure 4-33 shows the 1H NMR spectra of the (PB-b-PEO)3 star block copolymer before and after triethoxysilane hydrosilylation. The 1H NMR spectrum of the (PB-b-PEO)3 starting material was used to determine the distribution of 1,2and 1,4units in the polybu tadiene block. The two hydrogens of the pendant vinyl carbon in the 1,2-units (=CH2) and the other hydrogens in the double bonds (-CH=CHand CH=CH2) having chemical shifts of 4.9 ppm and 5.4 ppm, respectively, the PB block turned out to be composed of 75 mole % of 1,2-PB units. The 1H NMR spectrum of the (PB(Si(OEt)3)-b-PEO)3 star block copolymer reveal ed a strong decrease in the intensity of the signal corresponding to the -CH=CH2 ( = 4.9 ppm) protons of the pendant

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127 1,2-double bonds. Furthermore, the fact that the signal of the SiOCH2CH3 methyl protons increased in intensity ( = 1.2 ppm) indicated that the reacti on occurred with a high efficiency. However, as shown in Figure 4-32, some pe ndant double bonds remain after hydrosilylation. Based on the integration values of the signals at = 4.9 ppm (-CH=CH2) and = 0.5 ppm (-CH2Si-), a conversion of 85 % of the 1,2-PB pendant double bonds was found, knowing that triethoxysilane reacts predominan tly with the 1,2-PB units as previously demonstrated.312 This result was confirmed by IR spectroscopy (F igure 4-34). The abso rbance peak at 3100 cm-1 originating from CH=CH2 double bonds (=CH2 anti-symmetric stretch) disappears after hydrosilylation, but there are stil l remaining unreacted pendant double bonds as demonstrated by the signal at 1640 cm-1 (alkenyl HC=CH2 stretch) indicating less than 100% conversion. Study of the cross-linking reaction at the air/water interface. The air/water interfacial behavior of the chemica lly modified (PB(Si(OEt)3)-b-PEO)3 star block copolymer was first studied through isotherms at a subphase pH = 3.0 (Figure 4-35). Ini tially, the (PB(Si(OEt)3)-bPEO)3 star block copolymer was spread on the wate r surface, and the cross-linking reaction (pH = 3.0) was carried out for 10 hours at very larg e surface areas where no surface pressure was observed, then isotherms were recorded as shown in the lower curve of Figure 4-35. For comparison, the top curve illustrates the same copolymer spread and rapidly compressed at pH = 3 before any significant reaction could occur. The isotherm of the non-silylated (PB-b-PEO)3 starting material forms the central curve of Figure 4-35. It is first observed that the isotherm of the unreacted (PB(Si(OEt)3)-b-PEO)3 star block copolymer is shif ted to higher mean molecular area region compared to the non-hy drosilylated starting material. The shift to larger areas is in good agreement with the molecular weight in crease of the star block copolymer after hydrosilylation, with th e hydrosilylated star block copolym er molecules occupying a larger

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128 interfacial area. When the isothe rm is carried out 10 hours after the monolayer formation at pH = 3.0 (complete cross-linking), a si gnificant shift towards the low mean molecular area region was observed (loss of ethanol and wa ter molecules during hydrolysis and condensation, respectively) indicating that the material is more compact. A nother interesting feature is the lack of the pseudoplateau at 10 mN/m in the unreacted s ilylated material, and its reappearance upon crosslinking. This pseudoplateau corresponds to desorption of th e poly(ethylene oxide) chains from the surface to the aqueous phase below.298,299 We suppose that disappearance of the plateau is due to increased mixing between the EO units and the significantly more hydrophilic silylated units, while the crosslinking reac tion would appear to induce demi xing. The above interpretation is corroborated by the length of the PEO pseudoplateau A, which after cross-linking was 12,500 2 and compared well with that of the (PB-b-PEO)3 starting material at 12,080 2. These above observations were confirmed by recording is otherms at pH = 3.0 after different reaction times (Figure 4-36A). Fresh monolayers were spread for each experiment and the barrier compression speed was set to 100 mm/m in to prevent additi onal cross-linking during monolayer compression. As the reaction proceeds, the isotherms shift to the low mean molecular area region corresponding to a more compact cr oss-linked material with the PEO pseudoplateau becoming more and more pronounced. Before the cross-linking starts, both the hydrosilylated PB blocks and the PEO blocks are adsorbed at the interface with no PE O pseudoplateau. As the reaction proceeds, we suppose the area occupied by the hydrosilylated PB decreases whereas the fractional area occupied by the PEO stays the same. The reaction induces demixing of PEO chains which explains the more pronounced PE O pseudoplateau. This observation was also confirmed by plotting monolayer compressibility (K) versus mean molecular area for different reaction times (Figure 4-36B). Th e compressibility (K) was calculated from the expression (2):

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129 d dA A K 1 (2) where A is the mean molecular area and is the surface pressure. The development of the pseudoplateau can be observed with the increase of the comp ressibility peak corresponding to the PEO pseudoplateau transition ( = 10 mN/m) that also shifts towards the low mean molecular area region. The pH influence on the cross-linking reaction kinetics is shown by the isobar experiments carried out at = 5 mN/m and for different subphase pH values (Figure 4-37). The low surface pressure was chosen to avoid th e PEO phase transition. As expected, the MMA decreases faster for lower pH values. The isoba r at pH = 7.0 shows sl ow creep over time which demonstrates that the reaction is likely insignificant at this pH. At lower pH values the mean molecular areas overlap a nd stay constant after about 7 hours indicating completion of the crosslinking reaction. As for the hydrosilylated PB, the cross-linking reaction kine tics were slower in the case of triethoxysilane compared to the results obtained by Carino et al.263 for octadecyltrimethoxysilane (OTMS), which is consis tent with the slower elimination of larger alkoxy substituents. Once the cross-linking reaction was complete, th e cross-linked material could be removed from the interface with a spat ula after its compression to a final area of ca. 2 x 15 cm2 (Figure 438), approximately 50 monolayers thick. Unlike the (PB-b-PEO)3 star block copolymer, this material was self-supporting and gel-like and could be collected as elongated elastic sheets, which in turn could be drawn into very long fibers at high elongation (Fig ure 4-38). As expected, it was insoluble in common organi c solvents such as chloroform and THF, making molecular weight analysis by SEC impossible. It should be noted that this behavior was in sharp contrast to

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130 the films formed from AIBN, whic h could not be pulled from the surface as free standing films or fibers under any conditions attempted. Surface pressure influence on the morpho logy of the cross-linked material. The LB film morphologies obtained after cross-linking at different surface pressures were characterized by AFM after monolayer transfer to mica substrates (Figure 4-39 ). It is assu med that the monolayer morphologies are not modi fied during LB film formation as indicated by the transfer ratio values close to unity (T.R. = (Area of th e surface film transferre d) / (Area of the mica substrate)). As a control experime nt, it was first observed that at = 5 mN/m and pH = 7.0 (no cross-linking reaction), a smooth featureless monolayer with no phase separation between the hydrosilylated PB blocks and the PEO blocks is obtained (Figure 4-39A). After the hydrosilylation reaction, the PB block becomes mo re hydrophilic because of the triethoxysilane pendant groups and therefore is adsorbed at the air/water interface just like the PEO block. This interfacial property of the hydros ilylated PB block was also demonstrated with hydrosilylated PB homopolymers that formed stable monolayers for surface pressure s as high as 40 mN/m (Figure 4-27). Such behavior differs significan tly from the PB block of the (PB-b-PEO)3 star block copolymer which is much more hydrophobic and aggregates above the water surface. When LB transferred monolayers of the silylated block copolymer reacted under isobaric conditions for 10 hours at = 2 mN/m and pH 3.0 were examined by AFM (Figure 439B) a clear phase separation between the cross-linked material (yello w areas) and the poly(ethylene oxide) chains (dark areas) could be observed with the average he ight of the cross-linke d monolayer being about 2 nm. However it is only at surface pressures of about 6 mN/m and above that true PEO pores can be seen within the PB network (Figure 4-39 D). As the surface pressure increases, the average

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131 PEO pore size decreases (Figure 4-39D-G) to re ach a morphology with very small PEO domains trapped within a 2D cross-linked PB network ( = 9 mN/m; Figure 4-39G). For higher surface pressures such as 15 mN/m (Fi gure 4-39H), the cross-linked mate rial covers the entire surface with the PEO pores barely visible. This is in good agreement with the observation that PEO chains are pushed under the water surface at 10 mN/m. The topography was further investigated by sec tion analysis of the AFM images (Figures 4-40A and B). The height signal amplitude is significantly smaller for the image scanned for a surface pressure of 15 mN/m since the PEO pores are barely visible. The average sizes of the PEO pores obtained for different surface pressures we re roughly determined from the analysis of the power spectral density (PSD) (Figures 4-40C and D) of the surface morphology measured by AFM.329 The maximum of the large peak in th e PSDs corresponds to the average distance between nearest neighbor domains for non-porous material and the average size of the PEO pores for a porous material (Figure 4-40D). We observe that for a surface pressure of 5 mN/m, at which the cross-linked material is not porous, the approximate distance between two PB cross-linked domains is 180 nm. This characteristic po re size decreases with surf ace pressure applied during the cross-linking reaction from 130 nm for = 6 mN/m until it reaches a value in the range 40 nm for = 9 mN/m (Figure 4-40C). The curves for su rface pressures of 7 and 8 mN/m were not included for easier visualization, but the averag e PEO pore sizes for these surface pressure were found to be equal to 46 and 42 nm, respec tively. For higher surface pressure such as 15 mN/m, no maximum is observed for the PSD curve. This is in agreement with the fact that no PEO pores can be seen at this surface pressu re as shown by the AFM picture (Figure 4-39H). From these AFM images and the spectral power de nsity study, it can be concluded that with hydrosilylated PB blocks, the cr oss-linking reaction is more homogeneous than with AIBN,

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132 allowing the formation of a two-dimensional ge l with controlled PEO pore size by simply changing the polymerization surface pressure. The silane chemistry proceeds by a step growth mechanism which will favour homogeneous coupling over the entire surface in contrast to the chain growth mechanism of AIBN wh ich would favour nucleation spots. An experiment to illustrate retention of th e morphology after cross-li nking was attempted. The (PB(Si(OEt)3)-b-PEO)3 monolayer was cross-linked at constant surf ace pressure = 9 mN/m and pH = 3.0 (t = 10 hrs), and then the cross-li nked monolayer was tran sferred (Figure 4-41). A second transfer of the same cross-linked materi al was performed after the expansion of the system to = 2 mN/m. As shown by the images in Figure 4-41, the same morphology is observed before ( = 9 mN/m; pH = 3.0, t = 10h) and after expansion ( = 2 mN/m; pH = 3.0) with only a slight increase of the PEO pore size after monolayer expansion. A final experiment was attempted to prove th at for high surface pressures, the PEO chains are irreversibly displaced to the aqueous phase underneath the cross-lin ked PB network. After cross-linking the monolayer (t = 10 hrs, pH = 3.0) at 20 mN/m (surface pressure above PEO aqueous dissolution), the barriers were expanded and the isotherm of the resulting cross-linked monolayer was recorded as shown in Figure 4-42 (Blue curve). The PEO pseudoplateau is no longer present which indicates that the PEO chains were irreversibly positioned underneath the PB cross-linked network and could not readsorb at the interface during monolayer expansion. A control experiment was carried ou t by recording the isot herm of the monolayer cross-linked at 5 mN/m, that is below the surface pressure corr esponding to the PEO blocks aqueous dissolution (Figure 4-42, red curve). As expected, the PEO ps eudoplateau is still pres ent (even after several hysteresis cycles), which confirms that it is possible for high surface pressures ( > 10 mN/m) to

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133 freeze the thicker conformation (PEO sublayer underneath a PB network) of the cross-linked material. 4.4 Conclusion The main objective of this study was to propos e a new and general method to synthesize a novel two-dimensional polymeric nanomateria l consisting of a continuous cross-linked polybutadiene network containing po ly(ethylene oxide) pores of cont rolled sizes. To reach that goal, novel (PB(Si(OEt)3)-b-PEO)3 star block copolymers were synthesized by hydrosilylating the PB pendant double bonds of (PB-b-PEO)3 star block copolymers w ith triethoxysilane. The hydrolysis and condensation of the triethoxysilane pendant groups of the (PB(Si(OEt)3)-b-PEO)3 star block copolymer under acidi c conditions allowed us to eas ily crosslink the polybutadiene block directly at the air/water interface without any additives or reagents. This demonstrated the improved efficiency of this method compared to the radical polymerizati on in the presence of AIBN to get a homogeneously cross-linked mate rial with controlled and fixed morphologies. This strategy permits the control of the PEO pore size by simply adjusting the surface pressure during the cross-linking reaction as show n by AFM imaging of the LB films. The characterization of these 2D amphiphilic cross-linked materials are currently under investigation (permeability, small angle scattering, and 2D viscom etry) to understand the benefits provided by 2D self-assembly at the air/water interface over conven tional solution self-adsorption and other processes. At stake is the possibility to use 2D self-organization as a means to construct materials with anisotropic structures, to reproduc ibly engineer such stru ctures, and to target defined functions with these materials. In addi tion, such copolymer silanes monolayer could be easily transferred and grafted through covalent bonds to inorganic surfaces (glass support such as silicon wafer) for polymer/inorganic composite synt hesis. Work is also in progress to introduce triethoxysilane groups, and other metal alkoxides on other polydiene block copolymers of more

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134 complex architectures such as triblock copolymers with the aim toward the stabilization of other original 2D and 3D morphologies. Figure 4-1. Direct visualization of the 1% unreacted (A) and 0.05% cross-linked (B) wormlike micelles of PB45-b-PEO55 diblock copolymer by cryotransmission electron microscopy. Sketches illustrate the local structure of pristine and cross-linked PB cores. Use of a lower concentration in (B ) was necessitated by the gel-like character of the 1% cross-linked solution. Figure 4-2. Formation and osmotic deflation of PB46-b-PEO26 diblock copolymer, vesicles either without (A, B) or with (C) cross-linking between th e hydrophobic segments of butadiene.

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135 Figure 4-3. (A) Representation of the concept of a tw o-dimensional network of molecular pores, i.e., perforated monolayers. (B) Stabil ization of the resulting assembly via polymerization before and after tr ansfer to a macroporous substrate. Figure 4-4. A quasilinear coupler (a, p-xylylene dibromide), a cross-shaped monomer (b, lanthanum sandwich complex of tetrapyridyl porphyrin), an ideali zed structure (c), and an STM image (d) of a square grid. A) Poroussurfactant AIR Stabilization and Langmuir-Blodgett Transfer WATER Macroporous support B) CH2HgO2CCF3OR nCalix[n]arene n = 4, 5, 6 or 7 CH2HgO2CCF3OR nCH2HgO2CCF3OR nWater CH2Hg OR nCH2Hg OR n Y(CH2)mY LB transfer to macroporous supportWaterComposite Membrane A) Poroussurfactant AIR Stabilization and Langmuir-Blodgett Transfer WATER Macroporous support A) Poroussurfactant AIR Stabilization and Langmuir-Blodgett Transfer WATER Macroporous support B) CH2HgO2CCF3OR nCalix[n]arene n = 4, 5, 6 or 7 CH2HgO2CCF3OR nCH2HgO2CCF3OR nWater CH2Hg OR nCH2Hg OR n Y(CH2)mY LB transfer to macroporous supportWaterComposite Membrane Molecular poreCH2X OR n R = C2H5, n-C4H9, n-C8H17, or n-C16H33X=HgO2CCF3,C(=O)NHCH2CH2SSCH3, C(NH2)=NOH, C(=S)N(CH3)2, or CH=CH2 Molecular poreCH2X OR n Molecular poreCH2X OR n R = C2H5, n-C4H9, n-C8H17, or n-C16H33X=HgO2CCF3,C(=O)NHCH2CH2SSCH3, C(NH2)=NOH, C(=S)N(CH3)2, or CH=CH2

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136 Figure 4-5. (a) Amphiphilic porphyrins P1 and P2. P1: R = R1 (M = H2, Cu); P2: R = R2 (M = H2, Cu, Fe). (b) Amphiphilic porphyrazine P3 (M = Cu). Figure 4-6. (A) General reactions involved in th e polymerization of alkoxysilanes; (B) Pressurearea isotherms obtained for pH = 3.5 at 25 C after different reaction times; (C) Gelation of the OTMS monolayer as obser ved from Brewster angle micrographs. N N N N N N N N M a) b)R1 = O CH (CH2)19CH3 COOH R2 = N (CH2)19CH3 Br N N N N M R R R R R R R R Br Br Br Br R3 = C22H45 B) C) A)Hydrolysis Condensation 1 2O Si O O CH2 H+ HO Si HO OH CH2 + +3H2O -3CH3OH HO Si OH OH CH2 + + 16 16 16 HO Si OH OH CH2 HO Si HO OH CH2 +-H2O HO Si HO O CH2 Si HO OH CH2 16 16 1616 B) C) A)Hydrolysis Condensation 1 2O Si O O CH2 H+ HO Si HO OH CH2 ++3H2O -3CH3OH HO Si OH OH CH2 + + 16 16 16 HO Si OH OH CH2 HO Si HO OH CH2 +-H2O HO Si HO O CH2 Si HO OH CH2 16 16 1616

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137 Figure 4-7. Molecular structur e of the lipopolymer polymeriz ed by exposure to UV light. Figure 4-8. Surface Pressure-Area per polymer molecu le isotherms at 298K for (PB76-b-PEOn)4 star block copolymers (n = 57, 137, 444 and 1725). N N N CH2 O O H O 37% 20% 43% 10

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138 Figure 4-9. Isotherm of (PB76-b-PEO444)4 depicting how measurements of molecular area for the three principal regions are obtained. Figure 4-10. Linear dependence of Ap on the total number of ethylene oxide units.

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139 Figure 4-11. Linear dependence of Apseudoplateau on the total number of ethylene oxide units.

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140 Figure 4-12. Compression/expansion curv es for two different samples of PB4-b-PEO4 star block copolymers ((PB76-b-PEO57)4 and (PB76-b-PEO57)4) at (A) 5 mN.m-1, (B) 10mN.m-1 and (C) 15mN.m-1. 2x1053x1054x1055x105-1 0 1 2 3 4 5 Surface Pressure mN/mMean Molecular area (2)= 5 mN/m Cycle Order 5 1 (PB76b -PEO1725)450001000015000 -2 -1 0 1 2 3 4 5 Cycle Order 5 1 (PB76b -PEO57)4 = 5 mN/mSurface Pressure (mN/m)Mean Molecular Area (2)A)0 1x1052x1053x1054x1055x105-2 0 2 4 6 8 10 Surface Pressure (mN/m)Mean Molecular Area (2) (PB76b -PEO1725)4 = 10mN/m Cycle Order 5 1020004000600080001000012000 -2 0 2 4 6 8 10 (PB76b -PEO57)4 = 10mN/m Cycle Order 5 1Surface Pressure (mN/m)Mean Molecular Area (2) 020004000600080001000012000 0 2 4 6 8 10 12 14 16 Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle Surface Pressure (mN/m)Mean Molecular Area(2) Cycle Order 5 1 (PB76-b-PEO1725)4 = 15 mN/m020004000600080001000012000 0 2 4 6 8 10 12 14 16 Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle Surface Pressure (mN/m)Mean Molecular Area(2) Cycle Order 5 1 (PB76-b-PEO1725)4 = 15 mN/m Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle 010002000300040005000 -2 0 2 4 6 8 10 12 14 16 Cycle Order 5 1 Surface Pressure (mN/m)(PB76-b-PEO57)4 = 15 mN/m Mean Molecular Area(2) Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle 010002000300040005000 -2 0 2 4 6 8 10 12 14 16 010002000300040005000 -2 0 2 4 6 8 10 12 14 16 Cycle Order 5 1 Surface Pressure (mN/m)(PB76-b-PEO57)4 = 15 mN/m Mean Molecular Area(2)B) C)2x1053x1054x1055x105-1 0 1 2 3 4 5 Surface Pressure mN/mMean Molecular area (2)= 5 mN/m Cycle Order 5 1 (PB76b -PEO1725)450001000015000 -2 -1 0 1 2 3 4 5 Cycle Order 5 1 (PB76b -PEO57)4 = 5 mN/mSurface Pressure (mN/m)Mean Molecular Area (2)A)0 1x1052x1053x1054x1055x105-2 0 2 4 6 8 10 Surface Pressure (mN/m)Mean Molecular Area (2) (PB76b -PEO1725)4 = 10mN/m Cycle Order 5 1020004000600080001000012000 -2 0 2 4 6 8 10 (PB76b -PEO57)4 = 10mN/m Cycle Order 5 1Surface Pressure (mN/m)Mean Molecular Area (2) 020004000600080001000012000 0 2 4 6 8 10 12 14 16 Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle Surface Pressure (mN/m)Mean Molecular Area(2) Cycle Order 5 1 (PB76-b-PEO1725)4 = 15 mN/m020004000600080001000012000 0 2 4 6 8 10 12 14 16 Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle Surface Pressure (mN/m)Mean Molecular Area(2) Cycle Order 5 1 (PB76-b-PEO1725)4 = 15 mN/m Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle 010002000300040005000 -2 0 2 4 6 8 10 12 14 16 Cycle Order 5 1 Surface Pressure (mN/m)(PB76-b-PEO57)4 = 15 mN/m Mean Molecular Area(2) Firstcycle Second cycle Thirdcycle Fourthcycle Fifthcycle 010002000300040005000 -2 0 2 4 6 8 10 12 14 16 010002000300040005000 -2 0 2 4 6 8 10 12 14 16 Cycle Order 5 1 Surface Pressure (mN/m)(PB76-b-PEO57)4 = 15 mN/m Mean Molecular Area(2)B) C)

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141 Figure 4-13. Evolution of transfer ratio with the surface pressure in the case of (PB76-b-PEO1725)4 star block copolymer sample.

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142 Figure 4-14. AFM tapping mode amplitude images of the (PB76-b-PEO1725)4 (A, B, C, D, E, F, G and H) and (PB76-b-PEO57)4 (I and J) star block copolym ers transferred to a mica plate support at various surface pressures. The films are sc anned at a scan rate of 1Hz with a scale of 2 x 2 m (A, B, C, D, E and I) and 5 x 5 m (F, G, H and J). A) = 2 mN/m= 4 mN/mB)C) = 6 mN/m D) = 8 mN/m F) E) = 9 mN/m= 10 mN/m H) G) = 11 mN/m= 15 mN/m = 20 mN/m = 30 mN/mI) J) A) = 2 mN/m= 4 mN/mB)C) = 6 mN/m A) = 2 mN/m= 4 mN/mB)C) = 6 mN/m D) = 8 mN/m D) = 8 mN/m F) E) = 9 mN/m= 10 mN/m F) E) = 9 mN/m= 10 mN/m H) G) = 11 mN/m= 15 mN/m H) G) = 11 mN/m= 15 mN/m = 20 mN/m = 30 mN/mI) J) = 20 mN/m = 30 mN/mI) J)

PAGE 143

143 Figure 4-15. Dependence of the number of molecules pe r domain on the surface pressure in the case of the (PB76-b-PEO1725)4 star block copolymer samp le. The general trend shows that as pressure increases, more molecules aggregate (dramatic increase from = 4 mN/m) to form the observed circular PB microdomains.

PAGE 144

144 Figure 4-16. Model proposed to explain the forma tion of a network of elongated stripes. (a) Long PEO branches staying at the water surf ace as globules create a weak separation between the PB microdomains. (b) As th e surface pressure increases, the PEO blocks are pushed to the maximum hydration by a total extension of their chains on the surface of water. (c) Upon further compression, the PEO chains, too long to be totally submerge into the water subphase, shift to allow the PB microdomains to aggregate through only one point of c ontact to give el ongated stripes. Water subphase (a)PBdomains PEOchains PEOchains in extension 540 nm PB PEO PBelongated stripes (b) (c)= 2 mN/m= 8 mN/m= 15 mN/m Water subphase (a)PBdomains PEOchains PEOchains in extension 540 nm PB PEO PB PEO PBelongated stripes (b) (c)= 2 mN/m= 8 mN/m= 15 mN/m

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145 Figure 4-17. Surface Pressure-Area per polymer molecule isotherms for (PB200-b-PEOn)3 star block copolymers (n = 76, 326, 970, and 2182). Figure 4-18. Linear dependence of Apseudoplateau on the total number of ethylene oxide units.

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146 Figure 4-19. Surface Pressure-Area isotherms for (PB200-b-PEO76)3 star block copolymer before ( ) and after ( ) cross-linking in the presence of AIBN under UV light ( = 20 mN/m). Figure 4-20. IR spectra of (PB200-b-PEO76)3 before ( ) and after ( ) cross-linking in the presence of AIBN under UV light.

PAGE 147

147 Figure 4-21. AFM topographic images of the (PB200-b-PEO76)3 star block copolymer transferred to mica substrates ( = 20 mN/m) before (A) and afte r cross-linking (B, C, D, and E) at different reaction times. The f ilms are scanned with a scale of 10 x 10 m (A, B, C, and D) and 40 x 40 m (E). t = 0h t = 12h t = 18h t = 24h A) B) C) D) E)t = 24h t = 0h t = 12h t = 18h t = 24h A) B) C) D) E) t = 0h t = 12h t = 18h t = 24h A) B) C) D) E)t = 24h

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148 Figure 4-22. Hydrosilylation of the penda nt double bonds of the PB homopolymer. Figure 4-23. 1H NMR spectrum (CDCl3 ; 300MHz) of the commercial linear polybutadiene. H 22 182 + HSi(OCH2CH3)3 Toluene / 80 C / 24h 22 46 H 136Si H3CH2CO OCH2CH3 OCH2CH3 Pt

PAGE 149

149 Figure 4-24. 1H NMR spectrum (CDCl3 ; 300MHz) of the hydros ilylated polybutadiene. Figure 4-25. IR spectra of the polybutadie ne before and afte r hydrosilylation.

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150 Figure 4-26. Cross-linking reacti on involving hydrolysis and conde nsation of the triethoxysilane groups of the polybutadiene backbone. Figure 4-27. Surface pressure-Mean Molecula r Area isotherms of the hydrosilylated polybutadiene carried out after different reaction times (subphase pH = 3.0). O Si O O H+ HO Si HO OH ++3H2O -3EtOHHO Si OH OH + + HO Si OH OH HO Si HO OH + -H2OHO Si HO O Si HO OH : Polybutadiene backbone Hydrolysis Condensation

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151 Figure 4-28. Static elastic modulus-surface pressure curves of the hydrosilylated polybutadiene at different reaction times (subphase pH = 3.0). Figure 4-29. Mean Molecular Area-Time isobars of the hydrosilylated pol ybutadiene for various subphase pH values ( = 10 mN/m).

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152 Figure 4-30. (A and B) Removal of the cross-linked homopolymer from the Langmuir trough surface. The white material easily come s off the interface us ing a spatula. (C) Picture of the long cross-li nked fiber dried under vaccum. Figure 4-31. AFM topographic images of the LB films transferred onto mica substrates at = 10 mN/m: the commercial polybutad iene (A) and the hydrosilylated polybutadiene at pH = 7.0 (B; t = 0 h) and 3.0 for differen t reaction times (C ; t = 20 min and D; t = 10 h). (E and F) Cross-sectio n analysis of the images C and D. The images are 7 x 7 m2 (A) and 50 x 50 m2 (B, C, and D). A) B) C) A) B) C) B) D) C) A) F) E) B) D) C) A) F) E)

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153 Figure 4-32. Hydrosilylation of th e pendant double bonds of the (PB-b-PEO)3 star block copolymer.

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154 Figure 4-33. 1H NMR spectra (CDCl3 ; 300MHz) of (PB200-b-PEO326)3 star copolymer and the corresponding hydrosilylated (PB78-co-PB(Si(OEt)3)122-b-PEO326)3 star block copolymer.

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155 Figure 4-34. IR spectra of the (PB200-b-PEO326)3 star block copolymer and the corresponding hydrosilylated (PB78-co-PB(Si(OEt)3)122-b-PEO326)3 star block copolymer. Figure 4-35. Surface Pressure-Area isotherms for (PB200-b-PEO326)3 star block copolymer and the corresponding hydrosilylated (PB(Si(OEt)3)-b-PEO)3 star bl