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ADMET Amphiphiles

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Permanent Link: http://ufdc.ufl.edu/UFE0021932/00001

Material Information

Title: ADMET Amphiphiles
Physical Description: 1 online resource (149 p.)
Language: english
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2008

Subjects

Subjects / Keywords: admet, amphiphile, metathesis, peg, polyethylene
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: Acyclic diene metathesis (ADMET) allows for the synthesis of perfectly linear polyolefins with precisely controlled distribution of some exactly defined functional group, either within or pendant to the polymer backbone. The materials produced in this fashion possess properties that are tunable synthetically, accomplished by changing the identity of the regularly appearing moiety or the frequency of its appearance. A wide range of materials have been produced in this fashion, resulting in a catalogue of polymers displaying various morphologies and material responses. The ADMET polymerization and subsequent hydrogenation strategy when applied to the synthesis of model polymers facilitates the systematic study of various structural manipulations and their relationship to property. Here we describe the incorporation of hydrophilic pendant defects, namely short chain polyethylene glycol branches, onto the backbone of polyethylene using ADMET polycondensation chemistry. The motivation behind this work is to create semi crystalline materials, intentionally excluding this hydrophilic moiety from the crystal, thereby isolating the behavior of the methylene sequences between glycol branches. The immiscibility of the hydrophobic backbone and hydrophilic defects induces folding of the backbone about the pendant defect allowing the clustering of the PEG branches to minimizing contact between each segment. This work demonstrates that by carefully planning the identity of the pendant defect it can be excluded from the crystal and induced to aggregate; excluded and induced to crystallize separately, or excluded and re-included back into the polymer backbone crystals. The crystallization of the backbone excluding the PEG branches to the amorphous regions, or even the formation of bicontinuous PE and PEG phases could result in a layered or channeled morphology that may find utility in advanced applications.
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.
Thesis: Thesis (Ph.D.)--University of Florida, 2008.
Local: Adviser: Wagener, Kenneth B.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2008
System ID: UFE0021932:00001

Permanent Link: http://ufdc.ufl.edu/UFE0021932/00001

Material Information

Title: ADMET Amphiphiles
Physical Description: 1 online resource (149 p.)
Language: english
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2008

Subjects

Subjects / Keywords: admet, amphiphile, metathesis, peg, polyethylene
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: Acyclic diene metathesis (ADMET) allows for the synthesis of perfectly linear polyolefins with precisely controlled distribution of some exactly defined functional group, either within or pendant to the polymer backbone. The materials produced in this fashion possess properties that are tunable synthetically, accomplished by changing the identity of the regularly appearing moiety or the frequency of its appearance. A wide range of materials have been produced in this fashion, resulting in a catalogue of polymers displaying various morphologies and material responses. The ADMET polymerization and subsequent hydrogenation strategy when applied to the synthesis of model polymers facilitates the systematic study of various structural manipulations and their relationship to property. Here we describe the incorporation of hydrophilic pendant defects, namely short chain polyethylene glycol branches, onto the backbone of polyethylene using ADMET polycondensation chemistry. The motivation behind this work is to create semi crystalline materials, intentionally excluding this hydrophilic moiety from the crystal, thereby isolating the behavior of the methylene sequences between glycol branches. The immiscibility of the hydrophobic backbone and hydrophilic defects induces folding of the backbone about the pendant defect allowing the clustering of the PEG branches to minimizing contact between each segment. This work demonstrates that by carefully planning the identity of the pendant defect it can be excluded from the crystal and induced to aggregate; excluded and induced to crystallize separately, or excluded and re-included back into the polymer backbone crystals. The crystallization of the backbone excluding the PEG branches to the amorphous regions, or even the formation of bicontinuous PE and PEG phases could result in a layered or channeled morphology that may find utility in advanced applications.
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.
Thesis: Thesis (Ph.D.)--University of Florida, 2008.
Local: Adviser: Wagener, Kenneth B.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2008
System ID: UFE0021932:00001


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ADMET AMPHIPHILES


By

ERIK BENJAMIN BERDA


















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

UNIVERSITY OF FLORIDA

2008

































2008 Erik Benjamin Berda

































To Dana, the love of my life, for her sacrifices, love, support, and understanding and to Bethy,
Patty, and Mikey for lots of help along the way.









ACKNOWLEDGMENTS

There are many a great folken whom helped me along the way, both here in Gainesville

and back in Pennsylvania, say thankya. I'll start in Gainesville and work my way backwards in a

pseudo-chronological fashion.

First I'd like to acknowledge the Department of Chemistry, in particular Ben Smith, Ken

Wagener, John Reynolds, and Randy Duran. They saw potential when no other institution would

give me a chance. I am eternally grateful for your confidence.

I would again like to thank Ken Wagener for his patience; I am a stubborn and often

intolerable student. He forgave my frequent trespasses, and I learned a great deal about

mentoring from him. I would also like to acknowledge John Reynolds. It has been a pleasure

working under two capable advisors and I truly appreciate the opportunities I was presented with

working in the Butler Labs (a.k.a. the artist formerly known as Polymer Floor). Also I would like

to thank George Butler, rest peacefully, and his wife Josephine for their contributions to our

program. I would like to thank the rest of my committee: Bill Dolbier, Mike Scott, and Tony

Brennan for there time, effort, and advice. I would especially like to thank Bill Dolbier; I really

began to understand organic chemistry during his 5224 class. I would also like to acknowledge

Tammy Davidson and Eric Scriven, it has been a pleasure serving as a TA for both of you.

The road through Gainesville would not have been tolerable if it were not for great friends.

Thank you to Travis Baughman for splitting the rent, talking Wagener group, and rocking the

endless blues in E. Thank you to Jeremiah Tipton for the best rendition of Spoonman ever.

Thanks to Ben Reeves for low key low tones, the Wednesday jams are severely missed. Thanks

to his lovely wife Jenny for beating me Texas Hold'em repeatedly. Thank you to Josh McClellan

for philosophical discussions while nearly freezing to death in the November North Georgia

woods. Thanks to Piotr and Nela Matloka for good lunches, good parties, and being great hosts









in Belgium. I'd like to thank James Leonard for showing me that you can actually load 2 20 ga.

Rounds into a 12 ga. Shotgun, pull the trigger, and live to laugh about it. Thanks to Giovanni

Rojas for tons of laughs in Pasadena. I'd like to thank Flo Courchay for consistent kind remarks.

Thank you to Kate Opper for turtle sitting, dog lending, and spilling appletinis on my carpet.

Thank you to Sam Popwell for good laughs during the summer 07 teaching labs, What Would

Bear Do? Thank you to YuYing Wei for an analytical chemist's perspective on synthetic

chemistry, I'll stop cleaning spatulas with my gloves now. Thanks to Paula Delgado for showing

me the inherent flaws in the DSC sample press design. I would like to thank Zach Kean for good

times at T&T's. Thank you to the newest members of the Wagener Mafia: Bora and Brian, it was

nice to get to know you over the past several months. I'd like to thank Bob Brookins and Tim

Steckler for good laughs at the Seminole Hard Rock Casino. Thanks to The German for sharing a

few small pitchers between enormous chromatography sessions. Thank you to Pierre, Jianguo,

June, and Prasad for making 322/324 a great place to make polymers. Thanks to Merve Ertas for

constructive criticism and entertaining use of the English language. Thank you to Sophie Bernard

for being just sarcastic enough. I'd like to thank JJ Cowart for help with some polymerizations.

Also, thank you to Eva and Mike hanging out and listening to the Beatles. Thanks to Violeta

Petkovska for great conversation and even headed advice. I can't forget to thank Rachel Lande

for being a great student, even when I was not such a great mentor.

The gentle way kept me sane during my tour of duty in Gainesville. I would like to thank

Matt and Lauren, Davis and Virginia, Ed and Carissa, Thomas and Cathy, Larry and Ana,

Weber, Chris, Chan, and Natty for being great teachers and great friends. Thank you to the entire

UF Judo club past and present, it has been exceptional to train with such superb judoka.









Thank you to all of my colleagues from the Polymer Floor, Organic Division, and the rest

of the department that I may have inadvertently neglected to mention. I could fill an entire

dissertation thanking such a wonderful group of individuals.

Work would come to a grinding halt in this place if it weren't for the efforts of some

amazing administrative assistants. In the polymer office Sara Klossner and Gena Borrero, we

know who really runs the show, thank you for your hard work. Also, thank you to Lori Clark in

the Graduate Office and Maribel Lisk in the Chairman's office for all of your help as well.

Special thanks go to Toshio Masuda, Fumio Sanda, Masashi Shiotsuki, Kimiko Tada,

Kayo, Suzuki, Matty, the rest of the Masuda Lab, and Kazushi Mashima for being great hosts

and great friends during my trip to Kyoto. I can't wait to return.

From Pennsylvania there are a number of people to whom I am forever in debt. Of course,

my parents Pat and Marybeth, one couldn't ask for better teachers and friends. Also, thanks are

in order for my brother and best friend Mike Berda. I couldn't leave out Clarkie, thanks for all

your love and support, nor the GrandBerdas, thanks for the prayers. Of course this section

wouldn't be complete without thanking the rest of the "family," Jay DeFrangesco, Nick Pisano,

and Dan Watson. My mind wanders to Norristown circa 1997 often, thank you for being great

friends. In addition, I would like to thank Lynn Hinely, Joseph DeFrancesco, and Ron Petruso

for being great teachers and really shaping what would be my career choice.

From Penn State I would like to acknowledge Harry Allcock, Bob Morford, and Eric

Powell for my introduction to polymer research. Also, I would like to thank Bob Minard for

giving me a shot at teaching organic lab, also Dan Sykes for being a patient educator. I would

like to thank Steven Babcock for the only F I had to fight to recieve.









From Watts Hall to 333 thank you to Tom Riccairdi, Brian Boyle, Mark Lupinacci, Bryan

Koval, Aaron Pressman, Mike Carroll, Patty Salimone, Jessica Summers, and Hillary Ryan. My

memories of this time are fond and I think of you all often. I wouldn't have made it through PSU

without you. The thirty pounds I gained eating DP dough was worth it. I would also like to thank

Arie Hawkins and the crew at the college formerly known as WMC. Westminster Maryland was

an experience in and of itself.

Thank you to the I&C group at Limerick Generating Station, the opportunity to work here

was amazing and I will never forget it. I totally understand Dilbert and Office Space after this

experience.

From 1011 to UC building C I'd like to thank Geoff Faden, Jason Drews, E, Rob Lanning,

Steve Kulada, Tracey Johnson, Josie, Luis "Tito," Santana, Punishment, Ace, Tre Diggs, Laura

Merrick, and of course "Mecca." These times were unforgettable. The extra semester it cost was

worth it.

There are some people from Mario's that can not go unmentioned. Thank you to Melody

Phillips, Michelle, Scott, Ralph, Linda, Gail, and Tracey Faye; it was awesome to meet and work

with you. Of course I can not forget Tom at the end of the bar for good conversation over several

glasses of vino.

Mario's is special to me for another reason; this is where I met Dana. I knew from the

moment I met you. Thank you for your constant love and encouragement; you mean the world to

me. Of course I can't leave out my family on Elm Street: Denny, Judy, and Erin. Thanks for

sharing your lives; I am actually growing to enjoy playing board games.









Science is the pursuit of the truth; however the truth itself is unapproachable by any one

path. To me, this is the meaning of the degree Doctor of Philosophy; the art we choose is simply

the way we walk. My deepest gratitude for walking with me, I could not have done it alone.









TABLE OF CONTENTS

page

A CK N O W LED G M EN T S ................................................................. ........... ............. .....

L IST O F T A B L E S ..................................................................... ............................... 14

LIST OF FIGURES .................................. .. .... ..... ................. 15

ABSTRAC T ................................................... ............... 18

CHAPTER

1 INTRODUCTION ............... ................. ........... .............................. 20

T he E evolution of A D M E T ................................................................... ... ..........................20
Linear A D M ET Polyethylene............................ ........................................ ..... ..........23
Model Polyolefins with Precisely Placed Halogen Atoms.........................................24
Precise Fluorine Placem ent. .................................................................... ..................24
Precise Chlorine Placem ent. ................................................. ................................ 25
Precise Bromine Placem ent ............................... ........... ........... ............... 25
M odel Polyolefins with Precisely Placed Alkyl Branches ..................................................26
Precise Methyl Placement: ADMET Ethylene Propylene (EP) Copolymers..................26
ADMET Polyolefins with Larger Alkyl Defects.........................................................29
Precise Geminal Dimethyl Placement. ........................................ ......................... 29
Precise Ethyl Branch Placement ................................ ......... ..... ............... 29
Precise H exyl B ranch Placem ent....................... ..... .......................... ............... 30
Precise Ether Placem ent ........................................ ................. .... ..... .. 32
T ow ard A advanced A applications ..................................................................... ..................32
Precise Carboxylic Acid Placem ent. ........................................ ......................... 32
P precise Ionom ers ....................................................... 33
Purpose of Study ................................. ................................ ........ 34

2 ADMET AMPHIPHILES: POLYETHYLENE WITH PRECISELY PLACED
H Y D R O PH IL IC D E FE C T S ..................................................................... ........................49

Introduction ............ ........ .................................49
Experim mental Section................................................. 51
In strum entation ............................................................................... 5 1
M materials. .... ........ ........................... ..... ....... .............. ........ ....... .. .. .. 52
General Procedure for the Synthesis of Trityl Protected Tetra(ethylene glycol)
M onom ers ...................................... .... .. ..... ............... ... ...................52
2-(4-pentenyl)-6-heptenyl-1-tetra(ethylene glycol) monotrityl ether (2-2a)............53
2-(7-octenyl)-9-decenyl-1-tetra(ethylene glycol) monotrityl ether (2-2b) ..............53
2-(10-undecenyl)-12-tridecenyl-l-tetra(ethylene glycol) monotrityl ether (2-
2 c). ........................................................... .............................. 5 3
General Procedure for ADMET Polymerizations ................................. ...............54


9









Polymerization of 2-(4-pentenyl)-6-heptenyl-1 -tetra(ethylene glycol)
monotrityl ether (TEGOTr9u, 2-3a). ................................ .. .. .................54
Polymerization of 2-(7-octenyl)-9-decenyl-1-tetra(ethylene glycol) monotrityl
ether (TEG O Trl5u, 2-3b) .................................. ................. ........................ 54
Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tetra(ethylene glycol)
m onotrityl ether (TEG O Tr21u, 2-3c) ............................................................ 55
General Procedure for Parr Bomb Hydrogenation of Unsaturated Polymers .................55
TE G O Tr9 (2-4a) ..................................................... ........ .. ...... .... 55
TEGOTrl 5 (2-4b) ............................... .......... .................. 56
TEG O Tr21 (2-4c) ............................................................... .. .... ........... .. 56
General Procedure for the Removal of the Trityl Protecting Group .............................56
T E G O H 9 (2 -5a)................................................. ................. 56
TEG OH 15 (2-5b). ................................... .. ... ......... ............... 57
T E G O H 2 1 (2 -5c)........... ................................................................... .......... .. .. 57
R results and D iscu ssion ................... .... .............................. .. .... .......... .............. 57
Synthesis and Structural Analysis ............................................................................57
T h erm al A n aly sis....................................................................................................... 5 9
C o n c lu sio n s ..............................................................................6 2

3 PROBING THE EFFECTS OF PENDANT BRANCH LENGTH, DISTRIBUTION,
AND CONNECTIVITY IN ADMET AMPHIPHILES ............... ............................... 70

Intro du action ................... .......................................................... ................ 7 0
Experim ental Section................................................. 72
Instrum entation ..................................................................................................... 72
M materials ............................................. .. .... ....................... .................74
General Procedure for the Synthesis of Methoxy Terminated PEG Grafted Diene
M onom ers (3-3a-d, 3-4a-d).............................. ... ......... .................. ............ 74
9-(tetra (ethylene glycol) monomethyl ether)- 1,16-heptadecadiene
(6,6TE G O M e2, 3-3a)................................... ......................... .... ............. 74
12-(tetra (ethylene glycol) monomethyl ether)-1,22-tricosadiene
(9,9T E G O M e2, 3-3b). ..................... ............ .. .. .......................... ... ......... ... 75
9-(tri (ethylene glycol) monomethyl ether)-1, 16-heptadecadiene
(6,6T rE G O M e2, 3-3c). ....................... ............... .......................................... 75
12-(tri (ethylene glycol) monomethyl ether)-1,22-tricosadiene (9,9TrEGOMe2
3-3d) ................................ .................. ..... .......... 75
2-(7-octenyl)-9-decenyl-l-tetra(ethylene glycol) monomethyl ether
(6,6T E G O M e, 3-4a)...................... ........ ............ .. .. .. ..................76
2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) monomethyl ether
(9,9TEG OM e, 3-4b). ................ .............................................. .............. 76
2-(7-octenyl)-9-decenyl-l-tri(ethylene glycol) monomethyl ether
(6,6T rE G O M e, 3-4c). ................................................. .. ................ .........76
2-(10-undecenyl)-12-tridecenyl-l-tri (ethylene glycol) monomethyl ether
(9,9TrE G O M e, 3-4d). ................................. .... ...................... ............. 77
General Procedure for ADMET Polymerizations ............................. ...............77
Polymerization of 9-(tetra (ethylene glycol) monomethyl ether)-1,16-
heptadecadiene (TEGOMel5u2, 3-5a) .......................................................77









Polymerization of 12-(tetra (ethylene glycol) monomethyl ether)-1,22-
tricosadiene (TEGOM e21u2, 3-5b) ................................. ........................... 78
Polymerization of 9-(tri (ethylene glycol) monomethyl ether)-1,16-
heptadecadiene (TrEGOM el 5u2, 3-5c).............................................................78
Polymerization of 12-(tri (ethylene glycol) monomethyl ether)-1,22-
tricosadiene (TrEGOM e21u2, 3-5d)............................................................... 78
Polymerization of 2-(7-octenyl)-9-decenyl- -tetra(ethylene glycol)
monomethyl ether (TEGOM el 5u, 3-6a). .................................. ..... ................79
Polymerization of 2-(10-undecenyl)- 12-tridecenyl- -tetra (ethylene glycol)
monomethyl ether (TEGOMe21u, 3-6b). ..................... ...... ............... 79
Polymerization of 2-(7-octenyl)-9-decenyl-l-tri(ethylene glycol) monomethyl
ether (TrE G O M e 5u, 3-6c) ........................................................... ................... 79
Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tri (ethylene glycol)
monomethyl ether (TrEGOMe21u, 3-6d).....................................................79
General Procedure for the Hydrogenation of Unsaturated Polymers..............................80
TEGOM el52 (3-5a). ............................................... ...............80
TEGOM e212 (3-5b). ....................................................... ................. 80
TrEG O M e 152 (3-7c) .................. ............................. ........ .. ........ .... 81
T rE G O M e2 12 (3-7d)............ ............................................................ ........... .... 1
TEGOMel5 (3-8a) ....................................... ............81
TEG O M e21 (3-8b). ......................... .......................... .. ........ ...............8 1
TrE G O M el 5 (3-8c) .................. ...................................... .. ............
T rE G O M e2 1 (3-8d)............. .... ............................................................ .. .... .... .. 82
Results and Discussion .......................... ......... .. .......... ......... .... 82
Synthesis and Structural Analysis ............................................................................82
T h erm al A n aly sis....................................................................................................... 8 5
C o n c lu sio n s ..............................................................................8 8

4 INDUCING PENDANT BRANCH SELF ASSEMBLY IN ADMET AMPHIPHILES..... 100

In tro d u ctio n ................... ...................1.............................0
Experim ental Section................................................. 102
Instrum entation ............................................................................................... ....... 102
M a te ria ls ................................................. ................................................. .............. 1 0 3
Synthesis of 2-(10-undecenyl)-12-tridecenyl-l-tetra(ethylene glycol)-p-tosylate (4-
2 ). ........................................ .. ......................................10 3
General Procedure for Preparation of Monomers ...................................................... 104
2-(10-undecenyl)- 12-tridecenyl- 1 -tetra (ethylene glycol) methenyl pyrene
(9,9TEGOPy, 4-3a)...... ...................................104
2-(10-undecenyl)- 12-tridecenyl- 1 -tetra (ethylene glycol) mono n-hexyl ether
(9,9TEGOH ex, 4-3b) ..................... ............ ........... .. .......... ............. 10
2-(10-undecenyl)- 12-tridecenyl- 1 -tetra (ethylene glycol) mono n-tetradecyl
ether (99TEGOC14, 4-3c)........................................ ..................10
General Procedure for ADMET Polymerizations ........................................... ...106
Polymerization of 2-(10-undecenyl)- 12-tridecenyl- -tetra (ethylene glycol)
methenyl pyrene (TEGOPy21u, 4-4a) ............... ............ ..............................106









Polymerization of 2-(10-undecenyl)- 12-tridecenyl- -tetra (ethylene glycol)
mono n-hexyl ether (TEGOHex21u, 4-4b)..................................... ............... 106
Polymerization of 2-(10-undecenyl)- 12-tridecenyl- -tetra (ethylene glycol)
mono n-tetradecyl ether (TEGOC1421u, 4-4c). .............................................107
General Procedure for the Hydrogenation of Unsaturated Polymers............................107
T E G O Py2 1, (4-5a). ............................. .......................... ........... .... .......... 107
TE G O H ex2 1 (4-5b)............. ...................................................... ..... ...... ........ 108
TEGOC1421 (4-5c). ................................. .. .. .. ........ ...............108
R results and D discussion ................................................ .......... .. ........ .... 108
Synthesis and Structural A analysis ...................................................... .......... ....... 108
Therm al A analysis ............. ................................................................ ............... 111
C o n c lu sio n s .................................................................................................1 1 3

5 SYNTHESIS OF DEUTERIUM LABELED ADMET AMPHIPHILES ............................126

Introdu action ................... ......................................................................... 126
Experimental Section........... .... ....................... ........... 127
Instrum entation ............................................................................................... ....... 127
M a te ria ls ............................... ........................................................................................1 2 8
Synthesis of 99CD2TEGOM e (5-5).......................................................... ............... 128
Synthesis of 99TEGOCD3 (5-2) ......................................................... ............. 129
General Procedure for ADMET Polymerizations ............................... ...............130
C D 2T E G O M e2 1u ........................................................... .. .. ..................... 130
TEGOCD321u. ................................. ........ ........................ ...............130
General Procedure for the TSH Hydrogenation of Unsaturated Polymers .................130
C D 2T E G O M e2 1 (5-7). ............................................................ ......................... 13 1
TEGOCD321 (5-3). ....................................... ........ ...... .. .......... 131
Parr Bomb "Deuteration" of TEGOMe21d (5-1).................................................... 131
R results and D discussion .............................. ................ .......... .. .......... .. 132
Synthesis and Structural A analysis ...................................................................... 132
T h erm al A n aly sis.................................................. ................. 133
C onclu sions.......... .............................. ...............................................133

IM PRE SSION S ON LIFE IN K Y O TO .......................................................................... ... ... 138

H ajim e m a sh ite ................................................................................................................ 1 3 8
City life in Kyoto ..................................................................... ........ 139
G graduate School in K yoto .......................................................................... .................... 140
C college Sports at K yoto U university ......................................................................... ...... 141
B benefit to the U university of Florida......................................................................... ... ... 142
A rigato G ozaim ashita ................. ..................... .......... .. .. ........... .............. .. 143

L IST O F R E FE R E N C E S ................................................................................................ 144

B IO G R A PH IC A L SK E T C H ............................................... ............................. ..................... 149





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LIST OF TABLES


Table page

1-1 Effect of molecular weight on thermal behavior in linear ADMET polyethylene ............47

1-2 Precise halogen fam ily D SC data ........................................................... .....................47

1-3 Precise m ethyl fam ily D SC data....................... ......... ............................. ............... 47

1-4 Precise geminal-dimethyl family DSC data.................................... ....................... 47

1-5 Precise ethyl fam ily D SC data ......... ....................................................... ............... 48

1-6 Precise hexyl fam ily D SC data ............................................... ............................... 48

1-7 Precise ether fam ily D SC data ......... ....................................................... ............... 48

1-8 Precise carboxylic acid family DSC data ............................. .... ...............48

2-1 Molecular weight data for polymers described in chapter 2 ................ ......... ..........69

2-2 DSC data for polymers described in chapter 2. ..................................... ............... 69

3-1 Molecular weight data for polymers described in chapter 3......................... ...........99

3-2 DSC data for polymers described in chapter 3 ...................................... ............... 99

4-1 Molecular weight data for polymers described in chapter 4............. .................125

4-2 DSC data for polymers described in chapter 4. .................................... .................125









LIST OF FIGURES

Figure page

1-1 O lefi n m etathesis reactions ............................................................................... ........ 37

1-2 The ADM ET polycondensation reaction. ........................................ ....................... 37

1-3 W ell defined m etathesis catalysts ............................................. ............................. 38

1-4 The A D M ET m mechanism ....................................................................... ............... 38

1-5 ADMET polymerization/hydrogenation strategy for precision polyolefin models...........39

1-6 Nomenclature used in this introduction for ADMET polymers .....................................39

1-7 Precise halogen fam ily ......... ... .. .. .... .. ... ... ...................... ....39

1-8 Precise methyl family ................................. .... ..... .. ........ ......... 40

1-9 Synthesis of ADMET EP models. ............................ ...... ....... .................40

1-10 DSC comparison of random and precise EP polymers with similar branch content........41

1-11 Precise gem inal-dim ethyl fam ily ............................................... ............................ 41

1-12 Precise ethyl fam ily................................ .... .. ... .. ....... ..... .... 42

1-13 Precise hexyl fam ily ...................... ............ .. ... .......... ......... 42

1-14 DSC comparison of Et21 and Hex21 .............. .... .. ............................ ............... 43

1-15 Model for the crystallization of ADMET polyolefins with larger defects......................44

1-16 Precise ether fam ily............................... .. .................. .. ....... .... 44

1-17 DSC comparison of OM e21 and Et21 ........................... ..........................................45

1-18 Precise carboxylic acid fam ily ................................................. .......................... 45

1-19 Target morphology.......... ..................... ...... ...................46

2-1 Polym er Synthesis ....................................................... ............ ....... ..... 63

2-2 The 1H NM R spectrum of 6,6TEGOTr ............ .... ..... ................ ..................... 63

2-3 Progression of monomer (6,6TEGOTr) to polymer (TEGOH15) monitored by H
N M R ...........................................................................64




15









2-4 13C spectrum of T E G O H 15............................................................................... ........ 65

2-5 DSC heating and cooling profiles for TEGOH family. .............................................. 65

2-6 A nnealing TE G O H 15. ........................................................................... .......................66

2-7 MDSC of TEGOH15 ................. .........................................66

2-8 A nnealing T E G O H 2 1 ............................................................................. .....................67

2-9 X-ray diffraction pattern for TEGOH21 ............................... ...................67

2-10 IR spectrum of TEGOH15 and TEGOTrl5 ............. ............................................. 68

2-11 DSC comparisons for protected and deprotected polymers. A) TEGOTrl5 and
TEGOH15. B) TEGOTr21 and TEGOH21 .................................................................... 68

3-1 Model for chain folding and crystallization in ADMET amphiphiles............................. 90

3-2 A D M E T am phiphile synthesis .............................................. ......... ..............................90

3-3 1H NMR spectra of monomers 3-3a and 3-4a ............... ........ ..................91

3-4 13C NM R for monomers 3-3a and 3-4a...................................................................92

3-5 Assignment of aliphatic resonances in the 13C NMR spectra of monomers 3-3a and
3 -4 a .......................................................... ..................................... 9 3

3-6 Progression from monomer 4a to polymer 8a monitored by 1H and 13C NMR .................94

3-7 FTIR of TEGOM e21 and TEGOM e21u............................ ...................... ................94

3-8 DSC comparison of secondary A) and primary B) polymers with PEG grafts every
2 1st backbone carbon................ .................................... ...... ......... .. ............. 95

3-9 MDSC for TEGOMe21u A) and DSC annealing experiments for TEGOMe21u and
TrEGOM e21u B). ...................................................... .................... 96

3-10 DSC comparison of secondary A) and primary B) polymers with PEG grafts every
15th backbone carbon. .......................... .. ................ .......................................... ........ .97

3-11 Thermo gravimetric analysis of saturated polymers......... ......... ................. 98

4-1 Synthesis of polyethylene with precisely placed amphiphilic branches......................... 115

4-2 1H and 13C NM R spectra of 9,9TEGOTs (4-2) ..............................................................116

4-3 1H and 13C NMR spectra of 9,9TEGOPy (4-3a).......................................................117









4-4 1H and 13C NM R spectra of 9,9TEGOHex (4-3b) ................................. .... ..................118

4-5 1H and 13C NM R spectra of 9,9TEGOC14 (4-3c). .........................................................119

4-6 Expansion of the aliphatic regions of the 13C spectra of 9,9TEGOPy, 9,9TEGOHex,
and 9,9TEGOC14 (3a-c). ........................... ......... .. .. ..... .............. 120

4-7 Progression from monomer 4-3c to saturated polymer 4-5c monitored by NMR..........121

4-8 DSC heating and cooling traces for TEGOPy21u (4-4a) and TEGOPy21 (4-5a). ..........122

4-9 Absorption and fluorescence spectra for TEGOPy21 A) and TEGOPy21u B)............... 122

4-10 DSC heating and cooling traces for TEGOHex21u (4-4b) and TEGOHex21 (4-5b)......123

4-11 MDSC heating traces for TEGOHex21 (4-5b). ............. ...... ................... 123

4-12 DSC heating and cooling traces for TEGOC1421u (4-4c) and TEGOC1421 (4-5c).........124

5-1 Locations chosen for deuterium labeling in TEGOMe21 ........................ .............134

5-2 Synthesis of deuterium labeled TEGOM e21 analogues ......................... .................. 134

5-3 1H NMR of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe
show n for com prison ........................................................................... ......... ........... 135

5-4 13C spectra of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe
sh ow n for com p arison ........................................................................... ..................... 13 6









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

ADMET AMPHIPHILES

By

Erik B. Berda

May 2008

Chair: Kenneth B. Wagener
Major: Chemistry

Acyclic diene metathesis (ADMET) allows for the synthesis of perfectly linear polyolefins

with precisely controlled distribution of some exactly defined functional group, either within or

pendant to the polymer backbone. The materials produced in this fashion possess properties that

are tunable synthetically, accomplished by changing the identity of the regularly appearing

moiety or the frequency of its appearance. A wide range of materials have been produced in this

fashion, resulting in a catalogue of polymers displaying various morphologies and material

responses. The ADMET polymerization and subsequent hydrogenation strategy when applied to

the synthesis of model polymers facilitates the systematic study of various structural

manipulations and their relationship to property.

Here we describe the incorporation of hydrophilic pendant defects, namely short chain

polyethylene glycol branches, onto the backbone of polyethylene using ADMET

polycondensation chemistry. The motivation behind this work is to create semi crystalline

materials, intentionally excluding this hydrophilic moiety from the crystal, thereby isolating the

behavior of the methylene sequences between glycol branches. The immiscibility of the

hydrophobic backbone and hydrophilic defects induces folding of the backbone about the

pendant defect allowing the clustering of the PEG branches to minimizing contact between each









segment. This work demonstrates that by carefully planning the identity of the pendant defect it

can be excluded from the crystal and induced to aggregate; excluded and induced to crystallize

separately, or excluded and re-included back into the polymer backbone crystals. The

crystallization of the backbone excluding the PEG branches to the amorphous regions, or even

the formation of bicontinuous PE and PEG phases could result in a layered or channeled

morphology that may find utility in advanced applications.









CHAPTER 1
INTRODUCTION

The Evolution of ADMET

By the mid 1980s considerable advancements had been made in the field of olefin

metathesis chemistry.1 This mild carbon bond forming reaction was discovered by accident in the

late 1960s when researchers at Goodyear exposed a mixture of 1-olefins to a combination of

tungsten hexachloride and a lewis acid with the intent to find a new catalyst for the

polymerization of vinyl olefins.2 3 Instead of high polymer the research team observed a complex

mixture of scrambled olefin products. The mechanism of this reaction, first proposed by Yves

Chauvin4 in 1971 and later confirmed by Thomas Katz5 in 1975, involves the 2+2 cyclo addition

of an olefin to a metal carbene to form a metallocyclobutane, followed by a 2+2 cyclo reversion

to yield a new olefin and metal carbene. A majority of the research in the years to follow

involved the development of stable metal carbenes that could facilitate this useful

transformation, which has become an indispensable tool to the synthetic organic chemist (Figure

1-1).1,6

This reaction was used from its inception in the synthesis of polymers. Despite the lack of

well defined catalyst systems, a large volume of work had been produced by the mid 80s on the

ring opening polymerization of strained cyclic olefins.6 This reaction, coined ROMP (ring

opening metathesis polymerization) has become one of the most useful methods in the

fabrication of functionalized polymers for use in every imaginable application. Although it was

proposed early on that this reaction could also be used in the polycondensation of a linear

diolefin, it wasn't until 1987 when the first study proving the feasibility of this concept

appeared.' In this report the Wagener Group at the University of Florida attempted the

polymerization of 1,9 decadiene using an ill defined tungsten hexachloride /lewis acid mixture,









resulting in viscous oil and an intractable solid. Monitoring the disappearance of terminal olefin

signal via13C NMR and IR confirmed that the polymerization had occurred. Since any

polycondensation requires that the reaction involved proceeds quantitatively, the self metathesis

of styrene to stilbene was attempted as a test reaction. The isolated product in this case was

polystyrene, rather than stilbene, due to the cationic polymerization of styrene initiated by the

lewis acid present in the ill defined catalyst system. The authors were quick to realize that while

the concept was feasible, a well defined metal carbene catalyst would be necessary to prevent

this detrimental side reaction.

Fortunately, excellent progress was being made in catalyst design at this time. Professor

Wagener was so excited by the outlook for this reaction that he called Richard Schrock at MIT

and Bob Grubbs at Cal Tech to request assistance in the area of well defined catalysts and give

this acyclic diene metathesis (ADMET) a second try. Armed now with the right carbene for the

job, the Wagener group successfully synthesized stilbene from styrene in quantitative yields and

reported the first viable ADMET of 1,9 decadiene to polyoctenamer.8 Examples of well-defined

metal carbene metathesis catalysts are shown in Figure 1-3.

It was obvious even in the initial ADMET report that this reaction could have utility in the

fabrication of unique structures."' Virtually any moiety that can be functionalized with two

olefins could potentially become an ADMET monomer. Not surprisingly early efforts in the

Wagener group involved the synthesis of a variety of functionalized polymers using this

chemistry ("what could 'R' be"). As metathesis catalysts became increasingly robust and tolerant

of functional groups the number of moieties that could be used in this reaction increased and the

library of ADMET polymers grew considerably. Simultaneously, research on the mechanism of

this reaction ensued (Figure 1-4). By attacking ADMET from both practical and fundamental









aspects the Wagener research group was able to carve a niche in the olefin metathesis story.

Several review articles have been published on this topic.9-11

More recently research in the Wagener group has moved specifically towards the study of

precise structure (Figure 1-5). In particular, ADMET has the unique ability of producing

structures that mimic copolymers of ethylene and vinyl comonomers.9-20 These ethylene based

copolymers are typically made using chain propagation techniques, which are subject to

uncontrollable side reactions that create unwanted defects. These defects in turn have adverse

effects on polymer performance.9 Perfectly linear defect free model polymers can be created

using ADMET. This is accomplished by synthesizing a symmetrical terminal diene with a

pendant functional group, polymerizing, and exhaustively hydrogenating the resulting

unsaturated polyolefin backbone, allowing "defects" to be introduced in a controlled manner.

Knowing exactly what the identity of this defect is and where it occurs along the backbone

provides a systematic way to study this aspect of structure-property in ethylene based materials.9

This chapter describes the evolution of this study. Research on various materials from linear

polyethylene free of defects, through the addition of halogen atoms and alkyl branches of

increasing size has displayed that not only do the precise structures created using ADMET

possess unique properties, but that these properties are highly controllable. The library of

polymers that has been created in this fashion and the information these polymers have provided

about structure and property have led us to a new frontier: synthesis of precisely tunable

polyolefins for advanced applications. For simplicity of discussion, the polymers described in

this introduction will follow a systematic nomenclature: the identity of the pendant moiety is

named first, followed by its frequency of its appearance along the polyethylene backbone (Figure

1-6).









Linear ADMET Polyethylene

Unbranched, or perfectly linear, polyethylene is of considerable interest, particularly for

studying the behavior of this homopolymer during crystallization. Much of this work has been

conducted on large n-paraffins (monodisperse PE oligomers) up to 390 carbons long, since

defect free high-molecular weight PE is an elusive goal. While small molecule paraffin

compounds allow in-depth study of structurally perfect model materials, end group concentration

becomes a problem and leads to irregularities when trying to extrapolate morphological behavior

to a macromolecular system. The methyl endgroups present in n-paraffins are regarded as

defects that hinder crystallization. Polymer chains up to millions of grams per mol, on the other

hand, possess an infinitesimal number of methyl end groups relative to backbone carbons, and

comparisons between these two systems can lead to ambiguous results.

The synthesis of linear ADMET PE is important in this work to prove that the structures

created are indeed effective as models of the commodity materials they mimic. Perfectly linear

ADMET is prepared via the polymerization of 1,9 decadiene followed by saturation of the

product polyoctenamer with hydrogen. While high molecular weight samples exhibit thermal

behavior similar to that of high density polyethylene, molecular weights of products can be

controlled by regulating reaction time, temperature, and the monomer/catalyst ratio affording a

family of ADMET PE polymers with varied thermal responses. Despite the relatively low

molecular weight (between 2000 and 15000 g/mol) for some ADMET PEs, these polymers all

display sharp DSC melting transitions above 130 C (Table 1-1). While the peak melting point

increases with increased molecular weight, the polymer ofMn = 15,000 shows a peak melt of 134

C, exactly that of high density polyethylene. It is evident based on this work that beyond the









molecular weight threshold ofMn = 15,000 ADMET polymers can effectively model analogous

commercial materials.

Model Polyolefins with Precisely Placed Halogen Atoms

ADMET polyolefins with precisely placed halogen atoms (Figure 1-7) provide a unique

system for studying crystallization and melting behavior of precision polyolefins. By

synthesizing polymers decorated with fluorine, chlorine, and bromine the effect of this

systematic increase in pendant defect size can be probed. Four separate studies13' 14, 16,21 were

conducted on this class of materials. In the first the static methylene sequence length between

defects was held constant (18 backbone carbons) and the defect identity altered.16 In the other

three the defect was held constant (fluorine, chlorine, or bromine) and the distance between

defects altered.13, 14,21 In the first study it was found, not surprisingly, that with the increased

defect size came a decrease in melting temperature and enthalpy.16 When the defect identity was

held constant melting temperature and enthalpy decreased with decreasing distance between

defects,13, 14 the notable exception being the fluorine containing polymers which all have

approximately the same melting temperature despite differences in defect distribution.21 Table 1-

2 summarizes the DSC data for the precise halogenated polyethylenes.

Precise Fluorine Placement.

Regardless of branch distribution the melting points of ADMET polymers containing

precisely placed fluorine atoms are consistent with what is witnessed for linear ADMET PE,

evidence that the orthorhombic crystal structure of HDPE is unaffected by the addition of the

fluorine atom.21 This result was confirmed by WAXS. This is not surprising; considering the

similarity in size between hydrogen and fluorine the steric requirements for housing this defect in

the crystal shouldn't be significantly different. The melting enthalpy of this family of copolymers

does however decrease with increasing fluorine content. This is much more significant in the









cases of F15 and F9 than in the cases of F19 and F21. The decrease in enthalpy for the higher

defect concentration is evidence that electronic repulsions and bond polarity, as well as sterics,

play an important role in the crystallization behavior for ADMET polymers.16' 21

Precise Chlorine Placement.

The consequences for the incorporation of chlorine atoms at precise intervals along

polyethylene's backbone are more severe. There is a marked decrease in melting temperature

from ADMET PE and the precise fluorine family. There is also a change in crystal structure,

from orthorhombic to triclinic. These data show that the distribution of chlorine atoms in the

crystalline and amorphous regions is uniform. Further, the lamellar thickness (estimated using

atomic force microscopy) far exceeds the distance between defects on the backbone. This

confirms that the chlorine atoms are included within the crystal. The steric requirements,

however, are too severe for the orthorhombic crystal structure to remain intact. This behavior is

solely a result of the uniform defect distribution, as random analogues with similar branch

content possess broadened melting profiles with higher peak melting temperatures.22 This is

indicative of populations of lamella with different thicknesses, typical of copolymers with

random branch distribution and quite unlike the homopolymer type crystallization and melting

witnessed in ADMET systems. 13,21,22

Precise Bromine Placement.

ADMET models with precise bromine placement represent the upper size limit for our

study of halogen containing polymers, as nature resisted efforts to produce iodine containing

ADMET polymers. As expected, the increased size of the bromine atom results in a decrease in

melting temperature and enthalpy compared with the other halogenated ADMET polymers.14

Like the precision chlorine polymers a triclinic crystal structure was assigned for the bromine

containing polymers. The distribution of the bromine atoms was uniform in both crystalline and









amorphous regions like the chlorine polymers, and like the random chlorine polymers the

random bromine polymers exhibited copolymer type methylene sequence selection when

crystallizing.22 Based on AFM measurements, as is the case for chlorine, the bromine atom

resides within the crystal. Perhaps the most interesting feature of the precision bromine polymers

is their similarity in thermal response to ADMET polymers with precise methyl branch

placement (discussed in the following section). Based on these findings along with the data

reported for the fluorine polymers, it appears that defect steric requirements are the most

important factor in dictating the melting point of the resulting ADMET polymer crystal. Or,

more simply put: a defect is a defect, regardless of its identity.14 It could be a coffee cup!

Model Polyolefins with Precisely Placed Alkyl Branches

For more than half a century studies on structure and morphology have been central to

polyolefin research. Discoveries in this area have allowed for the synthesis of materials with

wide range of properties and behaviors. This is exemplified in the case of poly(ethylene-co-1-

olefins), where the behavior of the polymer can be greatly altered simply by varying the content

and identity of the comonomer chosen.

Precise Methyl Placement: ADMET Ethylene Propylene (EP) Copolymers.

Besides being commercially significant, EP copolymers can provide a general insight to

the structure property relationship when viewed as model systems. Consider polypropylene:

highly crystalline when the orientation of the pendant methyl group is highly regular

(syndiotactic or isotactic), however completely amorphous when backbone methyl groups are

randomly oriented (atactic); a simple structural difference resulting in significantly altered

behavior. Linear defect free polyethylene, the other extreme, is highly crystalline. However, this

crystallinity can be disrupted by the incorporation of defects, clearly evident in the

aforementioned halogen work. Between the extremes of amorphous attactic polypropylene and









highly crystalline, defect free polyethylene lie EP copolymers. Simply varying the amount and

placement of the incorporated methyl defect allows the response of the final material to be

significantly altered and ultimately controlled.9

Although numerous methods are available for producing model polymeric systems,

ADMET modeling controls comonomer content and distribution, therefore leading to fewer

ambiguities relative to other model systems when relating structure on the molecular level to

macroscopic properties.9' 19,23,24 Polymerization of symmetrical methyl branched terminal

dienes, followed by exhaustive saturation of the resultant polymer, afford these precise EP

models (Figure 1-8).19 These models are named according to the frequency of the pendant defect,

i.e. Me21 for a methyl branch every 21st backbone carbon, Mel5 for every 15th and so on. To

date Me5, Me7, Mel 1, Mel5, Mel9, and Me21 have been investigated. The syntheses of Mel 1

through Me21 are rather straight forward using this simple yet elegant

polymerization/hydrogenation approach.19 Placing branches every 5th or 7th backbone carbon

requires the synthesis of a symmetrical diene dimer, as the corresponding diene monomers

undergo ring closing metathesis rather than ADMET.24 Attempts to place methyl groups every

third backbone carbon, using a diene trimer, were unsuccessful due to the placement of the

methyl group in the allylic position. This allylic methyl decreases the yield of the cross

metathesis reaction allowing for only the partial oligermerization of the diene (Figure 1-9).25

The effects of branch distribution are clear when examining the thermal behavior of the

precision EP copolymer family.19 As defect content increases melting temperature and enthalpy

decrease. These precise models are semicrystalline even at branch contents high enough to

render random EP copolymers completely amorphous. Not until methyl groups are placed on









every 5th carbon do these precise ADMET EP copolymers lose the ability to crystallize.24 Table

1-3 summarizes the DSC data for the precise methyl family.

Copolymerization of ADMET EP monomers with 1,9 decadiene, thereby forming linear

EP copolymers with random branch distribution, has also been accomplished.23 In this study it

was again found that as the branch content increased, over all crystallinity as well as the melting

temperatures and enthalpies decreased. In the cases of the highest amount of branch

incorporation the random materials exhibited a broad, ill defined melting behavior quite unlike

the sharp melting endotherm observed for the precise models with similar branch content. This

drastic difference in the behavior between precise and random models punctuates the effect of

precise branch placement (Figure 1-10).19'23

Me21 and Mel5 have been further characterized by Wegner et al. using X-ray diffraction,

TEM, and Raman spectroscopy to further understand their structure and morphology.26 TEM

results indicate a lamellar thickness far exceeding the inter branch distance along the backbone,

proving that like chlorine and bromine atoms the methyl group must be included within the

crystal. The diffraction work elucidated crystal structure. This data showed that the chains pack

into a triclinic lattice which allows inclusion of methyl branches as lattice defects. Further, it was

found that methylene sequences between defects participate in a hexagonal sublattice. In order

for the chains to pack in this way the defects must be contained within plains oblique to the chain

stems, leading to conformationally distorted crystals. This is more prevalent in the case of Mel5

than in Me21 due to the greater defect content, a result confirmed by Raman spectroscopy. The

melting point depression witnessed is no surprise given these observations. Further scattering

experiments and exhaustive DSC experiments performed on Me21 by Wunderlich et al. lead to

the same conclusion involving defects concentrated in planes between stacks of hexagonally









packed methylene sequences; however a monoclinic lattice rather than triclinic was used to

describe the main unit cell within which the defects planes and hexagonal sublattice resides.27

ADMET Polyolefins with Larger Alkyl Defects.

To further understand the morphology of these precise materials and probe the size limit

for inclusion of defects within the crystal, ADMET models with precisely placed ethyl, hexyl,

and geminal dimethyl branches have been examined.

Precise Geminal Dimethyl Placement.

Precision geminal dimethyl ADMET models (Figure 1-11) display the effect increasing

steric bulk has on the polymer's thermal behavior.20 The addition of the second methyl group

when moving from Me9 to 2Me9 disrupts the polymers ability to pack into crystals resulting in

an amorphous material for 2Me9. Extending the inter defect sequence length to 14 or 20 carbons

renders the polymer semicrystalline with a depressed melting temperature when compared to the

analogous EP models. Interestingly, 2Mel5 shows much less melting point depression from

Mel5 than does 2Me21 from Me21. Further, 2Me21 shows thermal behavior unlike either

2Mel5 or any of the EP family. Exhaustive DSC studies on this material reveal that much of this

behavior is dependant on thermal history. WAXD studies show reflections associated with

hexagonal, monoclinic, and triclinic packing pointing towards polymorphism as a possible cause

of this complex behavior. The melting behavior was found to be incident with the melting of

eicosane (a 20 carbon n-paraffin), suggesting that crystallization behavior of 2Me21 is strongly

related to the branch to branch distance.27 The DSC data for this family of polymers is shown in

Table 1-4.

Precise Ethyl Branch Placement.

Ethylene butene (EB) copolymers featuring precisely placed ethyl branches (Figure 1-12)

were the next logical step in this study; moving from two single carbon defects to a single two









carbon defect.17 These are of particular interest as EB copolymers are important materials

commercially. Like 2Me9, Et9 is fully amorphous. Again, extending the space between defects

allows for crystallization in both Etl5 and Et21. Like the geminal dimethyl models the EB

models show greatly depressed melting temperatures when compared to the EP models. Another

point of interest is the difference in the observed thermal behavior from both the geminal

dimethyl family and the EP family. EB copolymers exhibit bimodal melting profiles very much

unlike the sharp, uniform melt exhibited by the EP family.17

WAXD investigations,17 as well as exhaustive DSC analysis27 have helped in explaining

this behavior. Like 2Me21, the melting behavior of Et21 can be correlated with that of eicosane

and is therefore very much dependant on the branch to branch distance. The WAXD results

shows some lattice expansion implying the partial inclusion of ethyl groups into the crystal,

however to a lesser extent than in EP21. Comparing these results for 2Me21 and Et21 imply that

much of the melting behavior is attributed to crystallization of methylene sequences between

defects. The bimodal melt could therefore be a result of polymorphism involving the inclusion

and exclusion of these defects, or a melting and simultaneous crystallization mechanism. In or

out of the crystal, the effect of increased volume requirements of the defect when increasing the

size by just one methylene unit is obvious. Table 1-5 summarizes the DSC data for the precise

ethyl family.

Precise Hexyl Branch Placement.

ADMET Ethylene Octene (EO) models serve as LLDPE models with precise hexyl branch

placement (Figure 1-13).12 These precise EO models follow a similar trend in behavior as the

previously discussed families; that is with increasing branch content decreasing melting

temperature and enthalpy are observed. It is no surprise that Hex9 is totally amorphous, as the

much smaller ethyl branch is able to completely disrupt crystallinity at this branch concentration.









A semicrystalline morphology is observed for Hex15; an interesting result considering all other

known EO copolymers with similar branch content are amorphous.12 Hex21 is as well

semicrystalline. The very low melting temperature (16 C) is indicative of very small crystallites.

Interestingly the melting enthalpy of Hex21 is similar to that of Et21, which is likewise

surprising considering the notable decreases in enthalpy from Me21 to 2Me21 to Et21. The

melting profile of the Hex21 closely mimics that of Me21 with a single sharp melting endotherm,

rather than the complex endotherms displayed by 2Me21 and Et21. One possible explanation is

that the hexyl branch is of sufficient size to be completely excluded from the crystal, owing the

observed behavior to the crystallization of the inter defect methylene units. The inclusion of the

branch resulting in a single crystal form as seen in Me21 is another possibility. With no

scattering data available for this polymer conclusions on whether or not the hexyl branch is

included or excluded from the crystal in these precise EO models based on thermal behavior

alone. Table 1-6 summarizes the DSC data for this group of polymers.

Some reasonable conclusions can be drawn by comparing the DSC heating traces of Et21

and Hex21 (Figure 1-14).12, 17 The lower melting mode of the bimodal melting endotherm for

Et21 perfectly overlaps with the melting endotherm for Hex21. Taking the similarity of melting

enthalpies into consideration as well is seems possible that at defect sizes beyond the ethyl group

the inter defect methylene sequences can crystallize and exclude the branch to the amorphous

regions. For these larger defects it would mean that these crystals do not organize into well

defined lamella as the ADMET EP's do. It is possible that there are fewer carbons in the

paraffinic crystal structure for Hex21 than for the other alkyl branched ADMET models (based

on the decreased melting temperature), where the defect itself as well as the point at which the

branch connects to the backbone would be excluded form this crystal, creating pockets of









uniform nanocrystallites randomly oriented in a matrix of amorphous hydrocarbon. This model

for the crystallization of ADMET polyolefins is illustrated in Figure 1-15.

Precise Ether Placement

Model polymers with the precise placement of ether moieties along a PE backbone (Figure

1-16) represent the first examples of linear ethylene-co-vinyl ether polymers ever made.28' 29

Difference in reactivity ratios between ethylene and vinyl ethers prevented the synthesis of this

type of material via chain propagation chemistry until very recently.30 These polymers differ

from their alkyl branched cousins only by the exchange of the methylene unit directly off the

backbone for an oxygen atom, which allows for some intriguing comparisons. Looking at the

thermal behavior of OMe21 and Et21, shown in Figure 1-10, reveals a very interesting result.9

The addition of the oxygen results in a slight increase of the peak melting temperature and

melting enthalpy. The melting temperature for OMe21, like several of the previous examples, is

incident with that of eicosane. As the steric requirements are roughly the same for these two

polymers it can be concluded that the polarity of the bond and the electronics of the oxygen

create a favorable place to initiate a fold in the polymer backbone, allowing for a more complete

crystallization of the inter defect paraffic unit cell. The DSC data for this group of precision

polyolefins are shown in Table 1-7.

Toward Advanced Applications

Precise Carboxylic Acid Placement.

A family of polymers with precise placement of carboxylic acids made using ADMET

(Figure 1-18) were synthesized to model commercial analogues.31 The resulting material

produced some very significant data concerning the morphology of ADMET polymers. One of

the most interesting features of these polymers is the fact that all of the carboxylic acid groups

are dimerized based on the FTIR spectra. Based on SAXS measurements on these polymers it









was found that they contain a high degree of order that corresponds directly to the inter defect

distance. WAXS data confirms that the paraffinic crystal structure is uninterrupted by the

incorporation of these defects. The melting point of COOH21, like the 2Me21, is incident with

eicosane. Correlating this data confirms that the methylene sequences between acids organize

into a paraffin like crystal with the dimerized carboxylic acids concentrated in defect planes,

similar to what was observed for the Me21. Diffraction experiments on a drawn sample of

COOH21 provide even more compelling evidence for this; several concentric reflections were

observed, corresponding to 1, 2, and 3 parallel stacks of crystallized inter-acid methylene

sequences. This behavior is in sharp contrast to that of the random analogues, again highlighting

the ability of ADMET to impart unique morphological features into polymeric systems by

perfectly controlling microstructure.31 Table 1-8 summarizes the DSC data for these polymers.

Precise lonomers

A family of precise ADMET ionomers was examined by neutralizing the above carboxylic

acid polymers with various amounts of zinc salt.32 As seen in the other ADMET studies

presented here, these materials did not behave at all like their random counterparts. In DSC

experiments the first heating trace of these materials resulted in liquid crystalline like

thermograms due to the melting of the well ordered interdefect paraffinic structures, resulting in

an LC like phase, before entering an isotropic melt. This behavior was not repeatable on

subsequent cooling and heating, implying that the ionic clusters and carboxylic acid dimers

dominate the morphology when the material is cooled after the initial heating cycle. Long term

annealing experiments were not conducted, however to see if the re-ordering of the inter defect

methylene sequences could occur.









Purpose of Study

The question of whether or not large defects are included or excluded from the crystals of

these ADMET polymers is central to our work in the Wagener research group. While the alkyl

branching work is interesting and provides insight into the unique behavior of ADMET

polymers, the composition of the defect is still identical to that of the backbone, and therefore

there remains the propensity for the inclusion of such a defect into the polymer unit cell. This

dissertation describes the incorporation of hydrophilic pendant defects, namely short chain

polyethylene glycol branches, onto the backbone of polyethylene using ADMET

polycondensation chemistry. The motivation in this work is to intentionally exclude the defect

from the crystal, thereby isolating the behavior of the inter defect methylene sequences. Phase

separation and self assembly of PE-co-PEG block copolymers and block oligomers is well

known.31-49 However this strategy has not been applied to precision polyolefins with any well

defined goal in mind. The immiscibility of the hydrophobic backbone and hydrophilic defects

should induce a specific behavior: the PE backbone chains should fold to allow the clustering of

the PEG branches, minimizing contact between each segment. The crystallization of the

backbone while excluding the PEG branches to the amorphous regions, or even the formation of

bicontinuous PE and PEG phases could result in a layered or channeled morphology (depicted by

a simple cartoon in Figure 1-19) that may find utility in advanced applications such as polymer

electrolytes or membrane technologies.

Chapter 2 describes the synthesis of a series of ADMET polymers with hydroxy terminated

PEG branches. A protecting group was used to ensure the absence of side reactions during

monomer synthesis and polymerization. The thermal behavior of the polymer with and without

the protecting group was evaluated; it was found that the identity of the graft end group can

significantly alter the behavior of these polymers. Analysis of the data collected for this family









revealed that the polymer backbone forms crystallites while excluding the PEG branches to

amorphous regions. Chapter 3 describes the synthesis of a series of ADMET polymers with

methoxy terminated glycol branches. Methyl groups are small enough as not to disrupt backbone

crystallization, but lack the ability for hydrogen bonding possessed by the polymers in chapter 2.

Three parameters are altered in this study: the length of the PEG graft, the manner in which the

branch is connected to the backbone, and the distribution of the branch along the backbone.

Doing so isolates the effect all three features have on the ability of the backbone to crystallize.

These polymers were analyzed both before and after hydrogenation to understand the effect the

site of unsaturation (essentially a defect) has on the crystallization of the backbone. Chapter 4

examines whether or not self assembly or aggregation of functional groups attached to the end of

the PEG chains is possible. This is an important question- if this concept is proven tailoring these

polymers for application has promise. First, the end of the PEG chain was labeled with a pyrene

unit. Fluorescence measurements confirm excimer formation and therefore the interactions of the

pyrene groups. Although this aggregation results in an increase in glass transition temperature

relative to the corresponding unlabeled polymer, the crystallinity of the polymer backbone

remains intact displaying that the amorphous content can be altered independently of the

crystalline regions. Two different n-paraffin end groups are also studied, the goal being to induce

self assembly of the branches and thus alter the crystallization behavior. This chapter

demonstrates that by carefully planning the identity of the pendant defect it can be excluded from

the crystal and induced to aggregate; excluded and induced to crystallize separately, or

cocrystallized with the polymer backbone crystals. Chapter 5 describes the synthesis of

deuterium labeled polymers analogous to the materials described in chapter three. By labeling

the polymer at 3 different locations information about molecular motion at these points above









and below the polymer's glass transition and melting temperatures can be accessed by solid state

deuterium NMR. The solid state NMR experiments themselves are, however, beyond the scope

of this dissertation and are therefore not discussed.









Olefin Cross
Metathesis


R1


R1


H R


H R2


R2


-R


-R2


R





R


Ring Closing
Metathesis



Ring Opening
Metathesis


Ring Opening
Metathesis
Polymerization


Acyclic Diene
Metathesis


R


R4


Figure 1-1: Olefin metathesis reactions


R


Metathesis
Catalyst


Removal of ethylene drives
equilibrium to the right

Figure 1-2: The ADMET polycondensation reaction.


- R4 +
\. Jn














PCy3
Cl RC

Cy3P
Cy3P


Schrock's Molybdenum
Catalyst


Grubbs' First Generation
Catalyst


C N YN -

Ct)
Cy3P

Grubbs' Second Generation
Catalyst


N -Y
4- N
CI/
Ru

0:)o


Grubbs Hoyveda
Catalyst


Figure 1-3: Well defined metathesis catalysts


L,,M-
R'


-R R-L -




R _LnM
H2C CH LnM R









S LnM:CH2 -- R-


Figure 1-4: The ADMET mechanism









R


n n


1. ADMET polymerization R
2. Exhaustive Hydrogenation
n n m


R

2n+2
2n+2


The Identity of group R and static methylene sequence n are
altered systematically to probe effects on polymer properties


Figure 1-5: ADMET polymerization/hydrogenation strategy for precision polyolefin models


R


"RxI n
x
"R(x+1)"


CH3


n
20
Me21


F15


Systematic nomenclature for ADMET polyolefins discussed in this
introduction. "Methyl 21" and "Fluorine 15" are illustrated as examples.

Figure 1-6: Nomenclature used in this introduction for ADMET polymers


m= 8,14,18,20

X= F, CI, Br


Figure 1-7: Precise halogen family

















x= 4,6,8,10,14,17,20


Figure 1-8: Precise methyl family


Catalyst



1. Polymerization
2. Hydrogenation



1. Polymerization
2. Hydrogenation





Catalyst
10.--


n=3 or more: polymerization
n=2 or less: ring closing metathesis





m
4



m
6


partial oligimerization,
no polymer formed


Figure 1-9: Synthesis of ADMET EP models. Shorter run lengths require the use of"ADMET
dimmers." The use of ADIMET trimers for placing groups every 3rd is complicated by
the presence of the allylic methyl groups.


n n
















26-

24-

E 22-
0
8 20-

18-
iL
16-

14-

12-

10-


CH3


Sequenced Copolymer
45 Branches/1000 Carbons








Random Copolymer
s.s 1 45 Branches/1000 Carbons
nt ,. .,,. ..- .


-40 -20 0 20 40 60 80 100 120
Temperature (C)


Figure 1-10: DSC comparison of random and precise EP polymers with similar branch content.


x= 8, 14, 20


Figure 1-11: Precise geminal-dimethyl family
















x= 8, 14, 20


Figure 1-12: Precise ethyl family


x= 8, 14, 20


Figure 1-13: Precise hexyl family

















1 .
.- Hex21

STm = 22 C


,..., 1 5 / i


I Tm= 16C
/ 4 1 = 48 J/g

L ------------------ .--------------
-a-,

I 40 -20 0 20 40 60

Temperature (C)


Figure 1-14: DSC comparison of Et21 and Hex21 (data taken consecutively on the same DSC
independent of references 13 and 18)











proposed ADMET
polyolefin crystal





-/


planes of
pendant
defects


7222Z1


similar crystallization and melting behavior

Paraffin crystal


~ o -v vvvv



planes of
end group
defects

Figure 1-15: Model for the crystallization of ADMET polyolefins with larger defects


x= 10 14, 20
R= Me, Et


Figure 1-16: Precise ether family










Ethyl branch every 21st carbon Methoxy group every 21st carbon
50 i ,


E 40-

0
*~ 30
LU ------ ----^ =

o 20
-LL0

-r 10 i


-50 -25 0 25 50
Temperature (0C)


75 100


Figure 1-17: DSC comparison of OMe21 and Et21


1 'X
x= 8, 14, 20


Figure 1-18: Precise carboxylic acid family










Placing a hyrdophilic defect --
on a hydrophobic backbone
should promote excusion of
the branch from the crystal
and induce phase separation


0o O y ,o possible 3-D
,, morphology
n








Sn = PEG Branch


Figure 1-19: Target morphology









Table 1-1: Effect of molecular weight on thermal behavior in linear ADMET polyethylene
Mn Polydispersity Tm (C) (peak) Ahm (J/g)
Index (PDI)
2400 2.4 130.7 252
7600 2.4 131.3 213
11000 1.9 132.0 221
15000 2.6 133.9 204


Table 1-2: DSC data for precise halogen family
Polymer Tm (0C)
F9 124
F15 124
F19 127
F21 124
C19 41
C1 15 63
C1 19 72
C121 81
Br9 -14
Brl5 49
Brl9 63
Br21 70


Table 1-3: DSC data for precise methyl family
Polymer Tm (OC)
Me5 Amorphous
Me7 -60
Me9 -14
Mell 11
Me15 39
Mel9 57
Me21 63



Table 1-4: DSC data for precise geminal-dimethyl family
Polymer Tm (0C)
2Me9 Amorphous
2Me15 32
2Me21 45


Ahm (J/g)
137
174
207
205
27
87
105
11
21
35
55
48


Ahm (J/g)

19
28
66
82
96
103


Ahm (J/g)
n/a
40
61









Table 1-5: DSC data for precise ethyl family
Polymer Tm (OC)
Et9 Amorphus
Etl5 -33 & -6
Et21 17&34 (ref 18)


Table 1-6: DSC data for precise hexyl
Polymer
Hex9
Hex 15
Hex21


family
Tm (OC)
Amorphus
-48
16


Table 1-7: DSC Data for precise ether family
Polymer Tm (0C)
OMell -41
OMel5 -10
OMe21 40
OEtl1 -4
OEtl5 -33
OEt21 28



Table 1-8: DSC data for precise carboxylic acid family
Polymer Tm (0C)
COOH9 Amorphous


COOH15
COOH21


Amorphous


Ahm (J/g)
n/a
Not reported
48


Ahm (J/g)
n/a
19
53





Ahm (J/g)
35
62
78
66
82
96


Ahm (J/g)
n/a
n/a
42









CHAPTER 2
ADMET AMPHIPHILES: POLYETHYLENE WITH PRECISELY PLACED HYDROPHILIC
DEFECTS

Introduction

Amphiphilic copolymers receive considerable attention in the literature due to the vast

array of compositions, morphologies, and properties available in these materials.3340 Systems

featuring hydrophilic segments, often poly(ethylene glycol) (PEG), and lipophilic segments such

as polyethylene (PE) are of interest due to their biocompatibility, propensity for phase

segregation, and ability to self assemble into higher ordered structures.3344 Block copolymer

architectures are by far the most investigated, which is not surprising as advances living

polymerization techniques have facilitated the synthesis of numerous systems with well defined

structures.35, 36, 38, 40, 41, 45-48 Amphiphilic graft copolymer architectures have received less

attention, likely due to the inability to control composition and structure with the same precision

available in block copolymer synthesis. This is particularly true for PE-g-PEG systems where

only a few examples exist, most of which lack structural control in terms of graft incorporation

or distribution.42

Well defined microstructures are essential to fully understand the behavior of amphiphilic

graft copolymer model systems. Acyclic diene metathesis (ADMET) polycondensation

chemistry is an excellent tool to model polymeric systems that lack such structural regularity

when synthesized through other means. A number of ethylene based copolymers have been

modeled in this fashion, from simple ethylene-co-ac-olefin systems made to mimic industrial

polyethylene9 to materials inaccessible through other means such as poly(ethylene-co-vinyl

ether)9 28 29 and so called "bio-olefins.49 50

The synthesis of PEG grafted unsaturated polyolefins with controlled placement of PEG

grafts has been previously reported.43 These polymers contained an overwhelming weight









percentage of polyether, and the properties reported reflected this. In that study the polyolefin

backbone remained unsaturated; this site of unsaturation in the backbone repeat unit serves as a

defect well known to impede the crystallization of PE.9 Recent success in controlling the

crystallization behavior and morphology of polyethylene through the incorporation of pendant

moieties of various size and polarity13, 14, 16, 28, 31 inspired this study, which investigates fully

saturated versions of these PEG grafted polyethylenes. This chapter describes the synthesis of a

family of polymers with short glycol chains (4 oxyethylene repeat units) attached every 9th, 15th,

and 21st carbon along a backbone of polyethylene. By precisely controlling structure, the relative

weight percentages of PE and PEG can be varied and the morphological effects of this

architecture systematically probed. The goal is that by incorporating a pendant group that is

immiscible with the PE backbone it may be possible to build a layered or channeled morphology

that would have utility in advanced applications.

The precise polymer structures have been confirmed by NMR (1H and 13C). Thermal

characterization by differential scanning calorimetry (DSC) reveals properties ranging from semi

crystalline to fully amorphous. When the PE and PEG content are nearly equal, the polymer

contains a high degree of amorphous content, as well as crystalline regions that display variable

melting behavior based on thermal history. For the case of the highest amount of polyether

incorporation, the material is completely amorphous. The lowest amount of polyether

incorporation results in a semicrystalline material; the melting temperature incident with n-

paraffin molecules of length similar to the static methylene sequence length between PEG

branches. X-ray diffraction experiments confirmed that the crystallinity is a result of the PE

backbone, which crystallizes excluding the PEG graft, creating crystalline phases of pure

polyolefin dispersed in a matrix of amorphous PEG and PE phases.









Experimental Section


Instrumentation.

All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian

Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to

residual signals from CDC13 (1H: 6= 7.27 ppm and 13C: 6 = 77.23 ppm) with 0.03% v/v TMS as

an internal reference. Thin layer chromatography (TLC) was performed on EMD silica gel

coated (250 |tm thickness) glass plates. Developed TLC plates were stained with iodine

adsorbed on silica to produce a visible signature. Reaction conversions and relative purity of

crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR)

measurements were conducted on polymer films cast from chloroform onto KBr plates using a

Bruker Vector 22 Infrared Spectrophotometer. High resolution mass spectrometry analyses were

performed on a Bruker APEX II 4.7 T Fourier Transform Ion Cyclone Resonance mass

spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization (ESI). The XRD

measurements were taken using a Philips X'Pert MRD system using grazing incidence

(omega=30). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA).

Molecular weights and molecular weight distributions (Mw\ ) were determined by gel

permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid

chromatography system with an internal differential refractive index detector (DRI) and two

Waters Styragel HR-5E columns (10 microns PD, 7.8 mm ID, 300 mm length) at 40 OC. HPLC

grade tetrahydrofuran was used as the mobile phase (flow rate = 1.0 mL/minute). Retention times

were calibrated against polystyrene standards (Polymer Laboratories; Amherst, MA).

Differential scanning calorimetry (DSC) and temperature modulated differential scanning

calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid









nitrogen cooling accessory calibrated using sapphire and high purity indium metal. All samples

were prepared in hermetically sealed pans (4-7 mg/sample) and were referenced to an empty pan.

Samples were run under s purge of helium gas. A scan rate of 10 C per minute was used unless

otherwise specified. Modulated experiments were scanned with a 3 OC per minute linear heating

rate with modulation amplitude of 0.4 C and period of 80 seconds. Melting temperatures are

taken as the peak of the melting transition, glass transition temperatures as the mid point of a step

change in heat capacity. Annealing experiments were conducted as follows: samples were heated

through the melt at 10 OC per minute to erase thermal history, followed by cooling at 10 OC per

minute to -150 C, heated at 10 OC per minute to the annealing temperature, held isothermally for

1 hour, cooled rapidly to -150 OC, and heated through the melt at 10 OC per minute. Data reported

reflects this final heating scan.

Materials.

Unless otherwise specified all reagents were purchased from Aldrich and used without

further purification. Grubbs' 1st generation catalyst was a gift from Materia, Inc. Diene tosylates

la-c and tetra(ethylene glycol) monotrityl ether were synthesized according to the literature.17' 19,

40, 44

General Procedure for the Synthesis of Trityl Protected Tetra(ethylene glycol) Monomers

Anhydrous DMF (250 ml) was cannula transferred into an oven dried, 3 neck round

bottom flask equipped with a magnetic stirrer, gas inlet, and charged with sodium hydride (1.3

eq, 60% dispersion in mineral oil). The slurry was cooled to 0C and 1.2 equivalents of tetra

ethylene glycol monotrityl ether in 30 mL of anhydrous DMF were added via syringe. Hydrogen

evolution was monitored by bubbler; when gas evolution ceased 1 equivalent of 1 in 30 mL of

anhydrous DMF was added via syringe. The reaction was stirred for 17 hours at 0 OC and

quenched by pouring into 600 mL of water. The resulting mixture was extracted with diethyl









ether and the combined organic washed with brine. Concentration afforded a yellow oil which

was further purified by column chromatography.

2-(4-pentenyl)-6-heptenyl-l-tetra(ethylene glycol) monotrityl ether (2-2a).

Column Chromatography: 55% diethyl ether 45% hexane eluent yielded 3.2g (55% yield)

of colorless oil. 1H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 9H), 1.98 (q, 4H), 3.21 (t, 2H), 3.29

(d, 2H), 3.50-3.75 (br, 14H) 4.98 (m, 4H), 5.82 (m, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR

(CDC13): 6 (ppm) 26.09, 30.83, 34.09, 37.86, 63.19, 70.15, 70.35, 70.44, 70.51, 70.56, 74.53,

86.28, 113.92, 126.68, 127.51, 128.48, 138.97, 143.91. ESI/HRMS: [M+NH4]+ calcd for

NH4C39H5205, 618.4153; found 618.4128. Anal. (CH) calcd for C39H5205: C, 77.96; H, 8.72.

Found C, 77.91; H, 8.82.

2-(7-octenyl)-9-decenyl-l-tetra(ethylene glycol) monotrityl ether (2-2b).

Column Chromatography: 25% ethyl acetate 75% hexane eluent yielding 4.0g (60% yield)

of colorless oil. 1H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (t, 2H), 3.29

(d, 2H), 3.50-3.75 (br, 14H) 4.98 (m, 4H), 5.82 (m, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR

(CDC13): .6 (ppm) 26.52, 28.71, 28.92, 29.70, 31.08, 33.58, 37.86, 63.09, 70.13, 70.36, 70.43,

70.50, 70.57, 74.54, 86.29, 113.90, 126.67, 127.52, 128.49, 138.98, 143.92. ESI/HRMS: [M]

calcd for C45H6405, 684.48; found 684.4753. Anal. (CH) calcd for C45H6405: C, 78.90; H, 9.42.

Found C, 78.96; H, 9.48.

2-(10-undecenyl)-12-tridecenyl-l-tetra(ethylene glycol) monotrityl ether (2-2c).

Column Chromatography 15% ethyl acetate 85% hexane eluent afforded 1.01g (34% yield)

of colorless oil. 1H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 1.98 (q, 4H), 3.21 (t, 2H), 3.29

(d, 2H), 3.50-3.75 (br, 14H) 4.98 (m, 4H), 5.82 (m, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR

(CDC13): 6 (ppm) 27.03, 29.14, 29.35, 29.71, 29.82, 29.85, 30.28 31.52, 34.01, 38.29, 63.51,









70.57, 70.78, 70.86, 70.92, 70.99, 74.98, 86.71, 114.28, 127.08, 127.92, 128.90, 139.41, 144.32

ESI/HRMS: [M+NH4]+ calcd for NH4C51H7605, 786.6031; found 786.6037. Anal. (CH) calcd

for C51H7605: C, 79.64; H, 9.96. Found C, 79.46; H, 10.03.

General Procedure for ADMET Polymerizations

Monomers were dried under vacuum at 80 OC for 48 hours prior to polymerization and

transferred to a 50 ml round bottom flask equipped with a magnetic stir bar. Grubbs 1st

generation catalyst (300:1 monomer catalyst ratio) was added and the flask placed under vacuum

at 45 C for 4 days. Polymerizations were quenched with ethyl vinyl ether (5 drops in degassed

toluene), precipitated into acidic methanol to remove catalyst residue, and isolated as an adhesive

gum.

Polymerization of 2-(4-pentenyl)-6-heptenyl-l-tetra(ethylene glycol) monotrityl ether
(TEGOTr9u, 2-3a).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 9H), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H),

3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDC13): 6 (ppm)

26.09, 30.83, 34.09, 37.86, 63.86, 70.72, 71.01, 71.13, 71.27, 71.33, 75.15, 86.67, 127.14,

128.15, 129.15, 130.06 (cis olefin), 130.79 (trans olefin), 144.68. IR (v cm-1) 2924, 2852,

1488, 1462, 1447, 1106, 1032, 1010, 966, 745, 760, 705. GPC (THF vs. polystyrene standards):

M, = 9100 g/mol; PDI (M. I ) = 1.89

Polymerization of 2-(7-octenyl)-9-decenyl-l-tetra(ethylene glycol) monotrityl ether
(TEGOTrl5u, 2-3b).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 21H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H),

3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDC13): 6 (ppm)

27.40, 27.84, 29.87, 29.95, 30.32, 30.40, 30.58, 31.96, 33.25, 38.71, 63.91, 70.93, 71.16, 71.23,

71.30, 71.37, 75.32, 87.09, 127.48, 128.32, 129.29, 130.15 (cis olefin), 130.90 (trans olefin),









144.71. IR (v cm-1) 2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 967, 746, 761, 706. GPC

data (THF vs. polystyrene standards): 3,, = 47300 g/mol; P.D.I. (If,, .\. ) = 1.85

Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tetra(ethylene glycol) monotrityl ether
(TEGOTr21u, 2-3c).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H),

3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR (CDC13): 6 (ppm) 27.08,

29.49, 29.80, 29.93, 30.33, 31.62, 32.87, 38.39, 63.56, 70.58, 70.81, 70.88, 70.95, 71.02, 75.08,

86.76, 127.10, 127.95, 128.95, 130.09 (cis olefin), 130.54 (trans olefin), 144.37 IR (v cm-1)

2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 967, 746, 761, 706. GPC data (THF vs.

polystyrene standards): M, = 49900 g/mol; P.D.I. (I1,, 11 ) = 1.71

General Procedure for Parr Bomb Hydrogenation of Unsaturated Polymers

Unsaturated, trityl protected polymers were dissolved in toluene and added to a glass lined

Parr bomb. Wilkinson's catalyst was added and the bomb charged with 700 psi of H2. The

reaction was stirred for 3 days at room temperature. The resulting polymers were purified by

precipitation into acidic methanol to remove catalyst residue and isolated as an adhesive gum.

TEGOTr9 (2-4a).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 17H), 1.98 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75

(br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDC13): 6 (ppm) 26.19,

30.86, 34.14, 37.82, 63.76, 70.63, 71.05, 71.17, 71.23, 71.41, 75.21, 86.63, 127.16, 128.12,

129.21, 144.68. IR (v cm-1) 2924, 2852, 1488, 1462, 1447, 1106, 1032, 1010, 745, 760, 705.

GPC (THF vs. polystyrene standards): /,, = 9300 g/mol; PDI (If,, /1, ) = 1.63









TEGOTrl5 (2-4b).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 29H ), 3.29 (t, 2H), 3.21 (d, 2H), 3.50-3.75 (br,

14H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDC13): 6 (ppm) 27.12, 30.03, 30.42, 31.62,

63.55, 70.57, 70.82, 70.90, 70.96, 71.03, 127.13, 127.97, 128.96, 144.38. IR (v cm-1) 2923,

2853, 1489, 1463, 1448, 1108, 1033, 1011, 746, 761, 706. GPC (THF vs. Polystyrene standards):

M, = 45100 PDI (Mw/l )= 1.99

TEGOTr21 (2-4c).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H ), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br,

14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDC13): 6 (ppm) 27.08, 29.98,

30.37, 31.62, 38.38, 63.57, 70.58, 70.82, 70.89, 70.96, 71.02, 75.02, 86.76, 127.11, 127.95,

128.95, 144.37 IR (v cm-1) 2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 967, 746, 761, 720,

706. GPC data (THF vs. polystyrene standards): M, = 51700 g/mol; P.D.I. (M.I/ ) = 1.77

General Procedure for the Removal of the Trityl Protecting Group

The saturated, trityl protected polymers 4a-c were dissolved in THF, acidified with

concentrated HC1, and refluxed for 5 hours. The resulting polymers were precipitated into

hexane to remove triphenyl methane and dried under vacuum at 80 OC over night to afford an

adhesive, elastic gum.

TEGOH9 (2-5a).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 17H ), 3.29 (d, 2H), 3.50-3.75 (br, 16H). 13C

NMR (d4-methanol): 6 (ppm) 26.75, 29.57, 30.53, 31.31, 38.29, 61.08, 70.28, 70.47, 72.56,

74.42. IR (v cm-1) 3424, 2924, 2854, 1465, 1351, 1116, 886, 722. GPC (THF vs. polystyrene

standards): 3f,, = 9500 g/mol; PDI (1f,, /., ) = 1.57









TEGOH15 (2-5b).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 29H ), 3.29 (d, 2H), 3.50-3.75 (br, 16H). 13C

NMR (d8-THF): 6 (ppm) 27.93, 30.76, 31.16, 32.52, 39.49, 62.29, 71.50, 71.62, 74.09, 75.03. IR

(v cm-1) 3423, 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards):

M, = 48700; PDI (M.\I ) = 2.13

TEGOH21 (2-5c).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H ), 3.29 (d, 2H), 3.50-3.75 (br, 16H), 13C

NMR (CDC13): 6 (ppm) 27.34, 29.95, 30.35, 31.55, 38.29, 62.00, 70.60, 70.87, 72.80, 75.04, IR

(v cm-1) 3422, 2923, 2852, 1463, 1351, 1114, 887, 720. GPC data (THF vs. polystyrene

standards): M, = 63200 g/mol; PDI (M\ / ) = 2.19

Results and Discussion

Synthesis and Structural Analysis

Synthesis of these precise amphiphilic copolymers involves well known chemistry (Figure

2-1). Diene tosylates 2-la-c (prepared as previously described19) were coupled with the PEG

branch via Williamson etherification. Tetra ethylene glycol (TEG) was monoprotected with the

bulky trityl (Tr) group before the Williamson etherification to avoid side reactions and enhance

solubility in organic media. The structures of monomer 2-2a-c were confirmed by NMR (1H and

13C), HRMS, and elemental analysis. Following polymerization the unsaturated, trityl protected

polymer was fully hydrogenated using Wilkinson's catalyst. The protecting group remained

untouched during this reaction and required subsequent acidification for removal. Polymer

structures 2-3a-c and 2-4a-c were confirmed by NMR (H and 13C) and FTIR. Molecular weight

data (GPC versus polystyrene standards) is summarized in Table 2-1.









For simplicity of discussion, a systematic nomenclature is used for these ADMET

amphiphilic copolymers and monomers. Monomers are named first by the number of methylene

carbons between the terminal olefin and branch point followed by the identity of the pendant

group, for example 6,6TEGOTr for structure 2-2b. Polymers are named first for the identity of

the pendant group, followed by the frequency of its appearance along the backbone, e.g.

TEGOH15 for structure 2-5b. Unsaturated polymers are denoted with the suffix "u." Figure 2-2

shows the 1H NMR spectrum of 6,6TEGOTr (arbitrarily chosen as an example) with peaks

assigned: trityl protecting group (7.2-7.6 ppm), terminal olefin (5.8 and 4.9 ppm), glycol protons

(3.5-3.8 ppm), branch point methylene unit (3.3 ppm), methylene unit adjacent to the protecting

group oxygen (3.2 ppm), allylic protons (2.1 ppm), and internal methylene protons (1.2-1.6

ppm).


The progression from monomer (6,6TEGOTr) to fully saturated, deprotected polymer

(TEGOH15) by 1H NMR is shown in Figure 2-3. After polymerization with first generation

Grubbs catalyst the terminal olefin signals at 4.9 and 5.8 ppm in the monomer spectrum

converge to one signal for internal olefin at 5.4 ppm in the spectrum of the unsaturated, protected

polymer 2-3b. Following hydrogenation, this internal olefin peak completely disappears in the

spectrum of the saturated but still protected polymer 2-4b. Deprotection with HC1 results in the

loss of trityl protecting group signal at 7.2-7.6 ppm as seen in the spectrum for the final polymer

2-5b. The pristine structures of the fully saturated, deprotected polymers were confirmed by 13C

NMR. The spectrum for polymer 2-5b is shown in Figure 2-4, only resonances predicted by the

repeat unit are present confirming the absence of side reactions and structural defects.









Thermal Analysis

Figure 2-5 shows the differential scanning calorimetry (DSC) cycle (first cooling scan

from the melt, second heating scan) for the series of saturated, deprotected polymers. TEGOH21

is semi crystalline with a peak melting temperature of 29 C. Decreasing the space between PEG

grafts when moving from TEGOH21 to TEGOH15 results in a decrease in melting temperature

from 29 C to -3 OC, as well as a decrease in melting enthalpy. Both polymers exhibit glass

transitions at the same temperature, -63 C. The marked change in the melting behavior coupled

with no change in the thermal response of the amorphous character implies that the crystallinity

is solely a result of the PE backbone. This is punctuated by the thermal behavior of TEGOH9,

where further decreasing the number of backbone carbons between grafts results in a completely

amorphous material. The glass transition temperature for TEGOH9, -65 C, is only slightly

depressed from the other polymers in this series, again indicating similar amorphous character. It

can be concluded when examining the whole series that for the case of TEGOH21 and

TEGOH15 the backbone of the polymer is able to form crystallites while totally excluding the

PEG grafts to the amorphous regions. In the case of TEGOH9, the close proximity of the PEG

groups along the backbone is disrupting the ability of the backbone to order into crystallites. All

three polymers therefore must contain amorphous regions with high polyether content, confirmed

by the nearly identical glass transitions. Table 2-2 summarizes the presented thermal data.

The melting profile of TEGOH15 is particularly interesting as it contains a second, lower

temperature endothermic shoulder. Since this material shows only a single, sharp crystallization

upon cooling this shoulder is surprising. Various annealing experiments were conducted to

further understand this behavior (Figure 2-6).

Annealing just below this shoulder induces a significant increase in its intensity without

altering the higher temperature endotherm. Annealing just above the shoulder completely









suppresses this behavior while slightly affecting the higher temperature endotherm. Annealing

first above, then below induces the same effect on the high temperature peak, but also the

reappearance of the lower temperature peak. These annealing treatments should decrease this

lower melting transition in all cases as the crystallites formed during cooling would provide the

template for crystal growth. The low temperature peak must therefore be an artifact of smaller,

less stable crystallites formed after the initial cooling scan.

This behavior was investigated in more depth using temperature modulated DSC (MDSC).

MDSC can provide a wealth of information on overlapping thermal transitions by separating

reversible and irreversible processes.51 Based on the MDSC plot (Figure 2-7), crystallization is

occurring simultaneously along with melting, beginning just above the glass transition

temperature. PE segments that are locked in the amorphous regions upon cooling gain sufficient

mobility to crystallize above Tg. As temperature increases this annealing process continues until

finally a maximum melting temperature is reached and the crystallites formed on cooling melt

with no simultaneous crystallization occurring. The low temperature peak is therefore a result of

these smaller crystallites undergoing an annealing process during heating, the higher temperature

peak due to the melting of crystallites formed during the cooling scan. Crystallization of the PEG

grafts can be ruled out as this phenomenon is not witnessed in the other polymers of this series.

Similar behavior is witnessed when annealing experiments are conducted on TEGOH21.

Annealing at room temperature for several days TEGOH21 results in an increase in peak melting

temperature, resulting in a melt that is incident with n-paraffin molecules with lengths similar to

the static methylene sequence length between grafts (Figure 2-8). This result provides more

compelling evidence that the crystallinity witnessed in these materials is wholly due to the PE

backbone.









Although thermal analysis can provide excellent information on the dynamic

crystallization behavior, it provides no information on the structure of the crystallites formed.

The thermal data strongly suggests that the PEG graft exclusion model is correct. To be certain

TEGOH21 was studied by x-ray diffraction. TEGOH21 was chosen over TEGOH15 because its

melting temperature allows for measurements to be taken at room temperature. The diffraction

pattern of TEGOH21 is shown in Figure 2-9.

A single diffraction is seen at 20= 21.60, which lies in between the known diffraction

patterns for orthorhombic paraffins27 and the (100)h reflection at 20=20.50 for hexagonal

polyethylene.52 This implies a contracted hexagonal unit cell tending towards the paraffinic

orthorohombic unit cell, almost identical to the results obtained by Wunderlich et. al. for

poly(octedecyl acrylate),27 also in agreement with Wegner' s26 assessment of precise alkyl

branched polyethylenes prepared by ADMET where the methylene sequences between branches

organize into a hexagonal sub lattice within a triclinic unit cell. By correlating the XRD and DSC

results obtained for these ADMET amphiphiles it can be concluded that the PE backbone is

indeed forming crystallites and excluding the glycol grafts to the amorphous regions.

The terminus of the PEG graft seems to play an extremely important role in this unique

behavior. Clustering of the PEG grafts, likely forming a pure polyether phase is evident by the

broad hydrogen bonding peak in the IR spectrum for these polymers (Figure 2-10).

Replacing the hydroxyl end group with the bulky trityl protecting group when going from

TEGOH15 to TEGOTrl5 disrupts all crystallinity and increases the glass transition temperature

by 30 C (Figure 2-11A). The results are similar when moving from TEGOH21 to TEGOTr21;

in this case crystallization is not totally disrupted, but it is significantly hindered as noted by a

decrease in melting temperature and enthalpy (Figure 2-11B). At this point it is unclear whether









the lack of hydrogen bonding, the shear steric bulk of the trityl group, or a combination of both

are responsible for the difference in behavior between the TEGOH and TEGOTr series.

Conclusions

In summary, amphiphilic PE-g-PEG copolymer models with precisely defined structures

can be synthesized via metathesis polycondensation chemistry; thermal data suggest that the PE

backbones crystallize excluding the PEG graft, a result that is confirmed by x-ray diffraction.

Thermal history has a significant effect on behavior of these materials. The identity of the graft

end group clearly plays an important role in the morphology of such systems; the copolymer can

be made semicrystalline or rendered completely amorphous simply by altering this group. The

following chapter describes the effects of changing the size of the PEG graft and the manner in

which it is connected to the backbone. Methoxy terminated PEG chains are examined to rule out

hydrogen bonding or end group steric requirements as the cause of the behavior witnessed in this

chapter. The effect of backbone saturation is also evaluated.










OTs


n n

1


n= 3(a)
6(b)
9(c)


/4uir
4






iv


iii


Figure 2-1: Polymer Synthesis. i: NaH, DMF, tetra ethylene glycol monotrityl ether; ii: Grubbs'
1st generation, 450C, vacuum; iii: Wilkinson's Catalyst, toluene, H2 700psi; iv: THF,
HC1.


D


A H
D


C
B


6.0 5.0 4.0 3.0 2.0 1.0


Figure 2-2: H NMR spectrum of 6,6TEGOTr.


EF


ppm 7.0














terminal
olefin


internal
olefin

Intra


no residual olefin


complete
deprotection


ppm 7.0 6.0 5.0 4.0 3.0 2.0 1.0

Figure 2-3: Progression of monomer (6,6TEGOTr) to polymer (TEGOH 5) monitored by 1H
NMR.


li!lhiC


-1










B


AF J
SG H 0


d8-THF


d8-THF


ppm 70 60 50 40 30

Figure 2-4: 13C spectrum of TEGOH15.


- r


0-


I 3-z
LL-
48 r

0 -


-100 -50 0 50


Temperature (oC)



Figure 2-5: DSC heating and cooling profiles for TEGOH family.




























-100 -50

Temperature (oC)


Figure 2-6: Annealing TEGOH15.


"~b ~ CP,~, ~ II
r~wwv/


reversing heat flow

total heat flow

non reversing heat flow

\, .____/


-150
-150


-100 -50
Temperature ("C)


Figure 2-7: MDSC of TEGOH15


'I
/











5-
4 OH
4- 4
10 n
no annealing


2 annealed at -20 C
I__ I

annealed at room
lemperalure for 1 month

I I


-BO -60 -40


-20 0 20 40
Temperature (oC)


60 80 100


Figure 2-8: Annealing TEGOH21


20 =21.6


10 20
2


Figure 2-9: X-ray diffraction pattern for TEGOH21.


Melting point of
C2H"42


30 40
(degree)


50 60





















U 70 V
E
U,
C 60-

S 50-

40-
-- TEGOH15 (lower curve)
30- TEGOTrl5 (top curve)

20-i i i i i i i
4000 3500 3000 2500 2000 1500 1000 500

v (cm1)




Figure 2-10: IR spectrum of TEGOH15 and TEGOTrl5 (arbitrarily chosen as examples)
showing clear hydrogen bonding stretch at -3500 cm-1 in 2-5b but absent in 2-4b.


-100 -80 -60 -40 -20 0
Temperature (C)


20 40 6O


-100 -80 -40 -20 0 20
Temperature (C)


Figure 2-11: DSC comparisons for protected and deprotected polymers. A) TEGOTrl5 and
TEGOH15. B) TEGOTr21 and TEGOH21.


40 s6 8










Table 2-1: Molecular weight data for polymers described in chapter 2.
Polymer Ma (kg/mol) /,, a (kg/mol) PDIb
TEGOTr9u 4.8 9.1 1.89
TEGOTrl 5u 25.6 47.3 1.85
TEGOTr21u 29.2 49.9 1.71
TEGOTr9 5.7 9.3 1.63
TEGOTrl 5 22.7 45.1 1.99
TEGOTr21 29.2 51.7 1.77
TEGOH9 6.1 9.5 1.57
TEGOH15 22.9 48.7 2.13
TEGOH21 28.8 63.2 2.19
a GPC vs. polystyrene standards; b 1I i., I



Table 2-2: DSC data for polymers described in chapter 2.
Polymer Tg (OC)) AC, (J/g-C) T, (OC) AHm (J/g) T, (OC) AH, (J/g)


TEGOH9
TEGOH15
TEGOH21


-65 .73 n/a
-63 .28 -3
-63 .26 29


n/a
-34
20


n/a
21
36









CHAPTER 3
PROBING THE EFFECTS OF PENDANT BRANCH LENGTH, DISTRIBUTION, AND
CONNECTIVITY IN ADMET AMPHIPHILES

Introduction

The manipulation of morphology via synthetic control over microstructure spearheads

research in polymer chemistry. The design of novel materials for advanced applications and the

study of commodity materials to improve commercial products both require an understanding of

the relationship between structure and material behavior. Acyclic diene metathesis (ADMET)

has been utilized extensively for the modeling of polymeric systems,9-11 where linear, defect-free

polymers produced by this method serve as pristine models of commercial materials or as novel

materials for advanced applications.13, 14, 31, 49, 53, 54 Research in this area has shown that imparting

these materials with such structural regularity results in behavior unique to this class of

polymers.9, 12, 13, 31, 53

A recent area of effort in our laboratory has been the synthesis of polyethylene with precise

placement of hydrophilic branches. Although these polymers resemble traditional amphiphilic

graft copolymers, there are a number of notable differences. First, ADMET amphiphiles possess

a perfectly uniform distribution of hydrophilic grafts (polyethylene glycol, PEG) along a

hydrophobic (polyethylene, PE) backbone, architecture which is typically inaccessible for PE-g-

PEG systems.39' 42, 55 The distance between branches (14 and 20 backbone carbons apart in this

study) is tunable synthetically by altering the size and symmetry of the diene monomer. Second,

the length of the graft is precisely defined, thereby differing from traditional amphiphilic graft

copolymers.39 42, 55, 56 Precise placement of hydrophilic branches on the hydrophobic backbone

induces a phase separated morphology that may be desirable in advanced applications.

Our recent synthesis of hydroxyl terminated tetra ethylene glycol grafted PE was the first

to demonstrate such morphological control.15 In that study we concluded that the polyethylene









backbone crystallized by excluding the PEG branch based on thermal and structural

investigations.15 We believe for this to occur, the PEG branch must be inducing a fold in the PE

backbone, thereby allowing for the clustering of the branches and allowing the backbone to form

small, isolated paraffin like crystallites (Figure 3-1). While the domain sizes that would result

from this model are quite small in comparison to other amphiphilic PE-co-PEG block and graft

copolymer systemss,3' 38, 39, 42, 55, 57 this behavior is well documented for alternating block

oligomers44,45, 58 of PEG and PE having blocks of similar size to the branch to branch distance

and PEG graft lengths of our polymers.

This chapter describes a family of polymers designed to test this model. First, the size of

PEG branch is altered. If the crystallinity is solely a result of the backbone then the

crystallization and melting behavior should be independent of branch length, which is indeed the

case. Second, if the folds in the chain are occurring at the site of the PEG branch then the manner

in which the branch is connected to the backbone should alter the behavior as well. In this report

we present polymers in which the first atom of the branch is either a carbon (methylene group) or

an oxygen atom. This alters both the sterics and electronics at this point in the chain thereby

altering the ability of the chain to fold, a result confirmed by thermal investigations. Finally,

altering the architecture of the backbone should effect changes in the behavior according to this

model. We examine this in two ways: by changing the static methylene sequence length between

branches and by investigating the effect a site of unsaturation (seen as a defect) has on the

crystallization and melting behavior. Both parameters prove significant in influencing the

behavior of the polymers presented.

The pristine nature of the monomer structures (shown in scheme 1) are confirmed by NMR

(1H and 13C), high resolution mass spectrometry, and elemental analysis. Corresponding









unsaturated and fully saturated polymer structures are confirmed by NMR (1H and 13C), and

FTIR. The thermal behavior is thoroughly investigated by differential scanning calorimetry

(DSC) and temperature modulated DSC (MDSC). The thermal stability of the materials is also

assessed using thermogravimetric analysis (TGA).

The thermal analysis results indicate that the architecture of the PE backbone as well as the

manner in which the PEG branch is connect to the backbone play an important role in the

crystallization and melting behavior of these materials. The size of the PEG branch, however,

does not affect this behavior. This provides compelling evidence that our model for the chains

folding about the defects, as presented in Figure 3-1, is correct.

Experimental Section

Instrumentation


All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian

Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to

residual signals from CDC13 (1H: 6= 7.27 ppm and 13C: 6 = 77.23 ppm) with 0.03% v/v TMS as

an internal reference. Thin layer chromatography (TLC) was performed on EMD silica gel

coated (250 ptm thickness) glass plates. Developed TLC plates were stained with iodine

adsorbed on silica to produce a visible signature. Reaction conversions and relative purity of

crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR)

measurements were conducted with a Bruker Vector 22 Infrared Spectrophotometer using

polymer films cast from chloroform onto KBr plates. High resolution mass spectrometry

analyses were performed on a Bruker APEX II 4.7 T Fourier Transform Ion Cyclotron

Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization

(ESI). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA).









Molecular weights and molecular weight distributions (Mw/Mn) were determined by gel

permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid

chromatography system with an internal differential refractive index detector (DRI) and two

Waters Styragel HR-5E columns (10 micron particle diameter, 7.8 mm ID, 300 mm length) at 40

C. The mobile phase was HPLC grade tetrahydrofuran at a flow rate of 1.0 mL/minute.

Retention times were calibrated versus polystyrene standards (Polymer Laboratories; Amherst,

MA).

Differential scanning calorimetry (DSC) and temperature modulated differential scanning

calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid

nitrogen cooling accessory and calibrated using sapphire and high purity indium metal. All

samples were prepared in hermetically sealed aluminum pans (4-7 mg/sample) and were

referenced to an empty pan. Samples were run under s purge of helium gas. Scan rates of

10C/min and 3C/min were used for DSC and MDSC, respectively. The MDSC modulation

amplitude and period were 0.4 and 80 s, respectively. Melting temperatures were evaluated as

the peak of the melting transition and glass transition temperatures as the mid-point of a step

change in heat capacity. Annealing experiments were conducted as follows: samples were heated

through the melt to erase thermal history, cooled at 10 OC per minute to -150 OC, heated at 10 C

per minute to the annealing temperature, held isothermally for 1 hour, cooled rapidly to -150 OC,

and heated through the melt at 10 OC per minute. The reported data reflect this final heating scan.

Thermogravimetric Analysis (TGA) was performed on a TA Instruments Q5000 IR using the

dynamic high-resolution analysis mode and a two point Curie temperature calibration (alumel

alloy and high purity nickel).









Materials.


Unless otherwise stated, all reagents were purchased from Aldrich and used without

further purification. Grubbs' 1t generation catalyst was a gift from Materia, Inc. Diene alcohols

3-la,b and 3-2a,b and oligoethoxy-p-tosylates were synthesized according to the literature.13' 17, 59

General Procedure for the Synthesis of Methoxy Terminated PEG Grafted Diene
Monomers (3-3a-d, 3-4a-d)

Anhydrous DMF (40 mL) was cannula transferred into an oven dried, 3-neck round-

bottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents

of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and 1

equivalent of 1 in 20 mL of anhydrous DMF was added via syringe. When gas evolution

(monitored by bubbler) ceased, 1.2 equivalents of 2 in 20 mL of anhydrous DMF were added via

syringe. The reaction was stirred for 17 hours at 0 OC and quenched by pouring into 600 mL of

water. The resulting mixture was extracted with diethyl ether and the combined organic washed

with brine. Concentration afforded a yellow oil which was further purified by column

chromatography.

9-(tetra (ethylene glycol) monomethyl ether)-1,16-heptadecadiene (6,6TEGOMe2, 3-3a).

Column Chromatography:40% ethyl acetate 60% hexane eluent yielding Ig (38% yield) of

colorless oil. 1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.35 (s,

3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H) 13C NMR (CDC13): .6 (ppm) 25.55, 29.08,

29.32, 28.89, 33.97, 34.16, 59.19, 68.23, 70.72, 70.84, 71.10, 72.16, 80.27, 114.35, 139.31.

ESI/HRMS: [M+NH4] calcd for NH4C26HsoOs, 460.3937; found 460.4048. Anal. (CH) calcd

for C26H5005: C, 70.54; H, 11.38. Found C, 70.38; H, 11.57.









12-(tetra (ethylene glycol) monomethyl ether)-1,22-tricosadiene (9,9TEGOMe2, 3-3b).

Column Chromatography:25% ethyl acetate 75% hexane eluent afforded .734g (30%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m,

1H), 3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): 6 (ppm)

25.63, 29.16, 29.35, 29.71, 29.79, 29.86, 30.07, 34.02, 34.19, 59.23, 68.19, 70.75, 70.83, 70.85,

71.11, 72.17, 80.35, 114.31, 139.42 ESI/HRMS: [M+NH4]+ calcd for NH4C32H6205, 544.4936;

found 544.4938. Anal. (CH) calcd for C32H6205: C, 72.95; H, 11.86. Found C, 73.48; H, 12.12.

9-(tri (ethylene glycol) monomethyl ether)-1,16-heptadecadiene (6,6TrEGOMe2, 3-3c).

Column Chromatography: 40% ethyl acetate 60% hexane eluent yielding 1.2g (51% yield)

of colorless oil. 1H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.35

(s, 3H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): .6 (ppm) 25.52,

29.05, 29.28, 28.84, 33.94, 34.12, 59.16, 68.18, 70.72, 70.79, 70.82, 71.06, 72.12, 80.24, 114.29,

139.28. ESI/HRMS: [M+Na]+ calcd for C24H4604 Na, 416.3734; found 421.3288. Anal. (CH)

calcd for C24H4604: C, 72.31; H, 11.63. Found C, 72.72; H, 11.64.

12-(tri (ethylene glycol) monomethyl ether)-1,22-tricosadiene (9,9TrEGOMe2 3-3d).

Column Chromatography: 25% ethyl acetate 75% hexane eluent afforded 1.01g (34%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m,

1H), 3.35 (s, 3H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): 6 (ppm)

25.56, 29.10, 29.30, 29.65, 29.73, 29.80, 30.01, 33.96, 34.13, 59.16, 68.14, 70.71, 70.77, 70.83,

71.06, 72.12, 80.27, 114.24, 139.32 ESI/HRMS: [M+ NH4]+ calcd for NH4C30H5804, 500.4673;

found 500.4676. Anal. (CH) calcd for C30H5804: C, 74.63; H, 12.11. Found C, 74.83; H, 12.37.









2-(7-octenyl)-9-decenyl-l-tetra(ethylene glycol) monomethyl ether (6,6TEGOMe, 3-4a).

Column Chromatography 40% ethyl acetate 60% hexane eluent yielding 1.03g (55% yield)

of colorless oil. 1H NMR (CDC3): 6 (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (d, 2H), 3.35

(s, 2H), 3.50-3.71 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): .6 (ppm) 26.90,

29.09, 29.28, 30.07, 31.48, 33.95, 38.26, 59.17, 70.55, 70.68, 70.75, 70.79, 72.81, 74.90, 114.27,

139.32. ESI/HRMS: [M+NH4]+ calcd for NH4C27H5205474.4153; found 474.4220. Anal. (CH)

calcd for C27H5205: C, 71.01; H, 11.48. Found C, 71.12; H, 11.67.

2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) monomethyl ether (9,9TEGOMe,
3-4b).

Column Chromatography: 25% ethyl acetate 75% hexane eluent afforded .560g (63%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H),

3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): 6 (ppm) 26.92,

29.06, 29.27, 29.63, 29.73, 29.76, 30.20, 31.45, 33.94,38.22, 59.13, 70.50, 70.64, 70.71, 70.75,

72.07, 74.88, 114.21, 139.29 ESI/HRMS: [M+NH4]+ calcd for NH4C33H6405, 558.5092; found

558.5088. Anal. (CH) calcd for C33H6405: C, 73.28; H, 11.93. Found C, 73.14; H, 12.05.

2-(7-octenyl)-9-decenyl-l-tri(ethylene glycol) monomethyl ether (6,6TrEGOMe, 3-4c).

Column Chromatography: 25% ethyl acetate 75% hexane eluent yielding 1.02g (60%

yield) of colorless oil. H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.29 (d, 2H),

3.35 (s, 2H), 3.50-3.71 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): .6 (ppm) 27.31,

29.49, 29.68, 30.47, 31.88, 34.35, 38.67, 59.52, 70.95, 71.09, 71.16, 71.20, 72.52, 75.29, 114.67,

139.70. ESI/HRMS: [M+NH4]+ calcd for NH4C25H4804 430.3891; found 430.3954. Anal. (CH)

calcd for C25H4804: C, 72.77; H, 12.72. Found C, 72.91; H, 12.88.









2-(10-undecenyl)-12-tridecenyl-l-tri (ethylene glycol) monomethyl ether (9,9TrEGOMe, 3-
4d).

Column Chromatography: 25% ethyl acetate 75% hexane eluent afforded .1.01g (55%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H),

3.35 (s, 3H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): 6 (ppm) 26.95,

29.09, 29.30, 29.66, 29.76, 29.79, 30.23, 31.49, 33.96, 38.26, 59.16, 70.53, 70.69, 70.75, 70.79,

70.83, 72.11, 74.91, 114.24, 139.33 ESI/HRMS: [M+NH4]+ calcd for NH4C31H6005, 514.4830;

found 514.4869. Anal. (CH) calcd for C31H6005: C, 74.95; H, 12.17. Found C, 74.83; H, 12.33.

General Procedure for ADMET Polymerizations

Monomers were dried under vacuum at 80 OC for 48 hours prior to polymerization and

subsequently transferred to a 50 mL round-bottom flask equipped with a magnetic stir bar.

Grubbs 1st generation catalyst (300:1 monomer:catalyst ratio) was added and the flask was

stirred under vacuum at 45 C for 4 days. Polymerizations were quenched with ethyl vinyl ether

(5 drops in degassed toluene), precipitated into cold, acidic methanol to remove catalyst residue,

and isolated as an adhesive gum.

Polymerization of 9-(tetra (ethylene glycol) monomethyl ether)-1,16-heptadecadiene
(TEGOMel5u2, 3-5a).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H),

3.50-3.75 (br, 16H), 5.35 (m, 2H). 13C NMR (CDC13): .6 (ppm) 25.63, 27.44, 29.47, 29.90,

29.97, 32.82, 34.23, 59.21, 68.20, 70.72, 70.82, 70.84, 71.94, 72.16, 80.35, 130.04 (cis olefin),

130.50 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs.

Polystyrene standards): M, = 88700 ; PDI (M/. I) = 1.75









Polymerization of 12-(tetra (ethylene glycol) monomethyl ether)-l,22-tricosadiene
(TEGOMe21u2, 3-5b).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H),

3.50-3.75 (br, 16H) 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 25.67, 27.36, 29.46, 29.58, 29.77,

29.87, 29.92, 30.02, 30.12, 32.85, 34.22, 59.24, 68.19, 70.74, 70.83, 70.85, 71.11, 72.17, 80.38,

130.05 (cis olefin), 130.54 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886,

721. GPC (THF vs. Polystyrene standards): f,, = 114500 ; PDI (I ,, /.\ = 1.78

Polymerization of 9-(tri (ethylene glycol) monomethyl ether)-1,16-heptadecadiene
(TrEGOMel5u2, 3-5c).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H),

3.50-3.75 (br, 12H), 5.35 (m, 2H). 13C NMR (CDCl3):.6 (ppm) 25.63, 27.44, 29.47, 29.90, 29.97,

32.82, 34.23, 59.22, 68.21, 70.67, 70.82, 70.87, 71.11, 72.17, 80.34, 130.09 (cis olefin), 130.51

(trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs.

Polystyrene standards): M, = 79500; PDI (M/\ ) = 1.85

Polymerization of 12-(tri (ethylene glycol) monomethyl ether)-1,22-tricosadiene
(TrEGOMe21u2, 3-5d).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H),

3.50-3.75 (br, 12H) 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 25.67, 27.44, 29.44, 29.56, 29.76,

29.86, 29.91, 30.01, 30.11, 32.84, 34.22, 59.22, 68.16, 70.77, 70.82, 70.87, 71.10, 72.17, 80.36,

130.07 (cis olefin), 130.53 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886,

721. GPC (THF vs. Polystyrene standards): f,, = 108700 ; PDI (T /. I = 1.69









Polymerization of 2-(7-octenyl)-9-decenyl-l-tetra(ethylene glycol) monomethyl ether
(TEGOMel5u, 3-6a).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (d, 2H), 3.35 (s, 2H),

3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDC13): .6 (ppm) 26.60, 27.02, 29.06, 29.52,

29.78, 31.16, 32.43, 37.92, 58.79, 70.15, 70.29, 70.36, 70.39, 71.72, 74.51, 129.89 (cis olefin),

130.08 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs.

Polystyrene standards): 3/,, = 100400 ; PDI (- f, /.1, I = 1.74

Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) monomethyl
ether (TEGOMe21u, 3-6b).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.35 (s, 3H),

3.50-3.75 (br, 16H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 27.03, 29.45, 29.76, 29.81, 29.90,

30.00, 30.32, 31.54, 32.83, 38.30, 59.22, 70.55, 70.71, 70.76, 70.80, 72.12, 74.96, 130.05 (cis

olefin), 130.52 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC

(THF vs. Polystyrene standards): M, = 96200 ; PDI (M/ 1 ) = 1.76

Polymerization of 2-(7-octenyl)-9-decenyl-l-tri(ethylene glycol) monomethyl ether
(TrEGOMel5u, 3-6c).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (d, 2H), 3.35 (s, 2H),

3.50-3.71 (br, 12H), 5.35 (m, 2H). 13C NMR (CDC13): .6 (ppm) 27.02, 27.09, 29.48, 29.94,

30.20, 31.59, 32.85, 38.35, 59.22, 70.58, 70.74, 70.79, 70.85, 70.87, 71.16, 74.94, 130.06 (cis

olefin), 130.51 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC

(THF vs. Polystyrene standards): /,, = 37200 ; PDI (T ,, /. ) = 1.74

Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tri (ethylene glycol) monomethyl ether
(TrEGOMe21u, 3-6d).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.35 (s, 3H),

3.50-3.75 (br, 12H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 27.06, 27.51 29.46, 29.78, 29.83,









29.92, 30.34, 31.57, 32.85, 38.35, 59.24, 70.58, 70.75, 70.80, 70.84, 70.88, 72.16, 74.97, 130.08

(cis olefin), 130.54 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC

(THF vs. Polystyrene standards): 1/,, = 57700 ; PDI (3 ,, .\ ,) = 1.72

General Procedure for the Hydrogenation of Unsaturated Polymers

Unsaturated polymers were dissolved in dry o-xylene. p-toluenesulfonyl hydrazide (TSH)

and tripropyl amine (TPA) were added with stirring (3 equivalents each). The resulting solution

was refluxed for 3-4 hours while monitoring nitrogen evolution with a bubbler. When gas

evolution ceased, the solution was cooled to room temperature, an additional 3 equivalents of

TSH and TPA were added, and the solution was refluxed for another 3 hours. The solutions were

then concentrated to one-half of the original volume and precipitated into cold, acidic methanol.

The polymers were isolated as elastic, adhesive gums.

TEGOMel52 (3-5a).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 28H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br,

16H). 13C NMR (CDC13): .6 (ppm) 25.67, 29.93, 30.12, 34.22, 59.21, 68.18, 70.72, 70.82, 71.09,

72.16, 80.35. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene

standards): M, = 92200 ; PDI (M/.\ )= 1.71

TEGOMe212 (3-5b).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 40H), 2.01, 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75

(br, 16H). 13C NMR (CDC13): 6 (ppm) 25.68, 29.96, 30.12, 30.12, 34.22, 59.23, 68.19, 70.74,

70.85, 71.11, 72.17, 80.38. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs.

Polystyrene standards): M, = 127500 ; PDI (M/\ ) = 1.44









TrEGOMel52 (3-7c).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 28H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br,

12H). 13C NMR (CDC13): .6 (ppm) 25.67, 29.93, 30.12, 34.23, 59.22, 68.19, 70.76, 70.82, 71.11,

72.18, 80.37. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene

standards): M, = 86700 ; PDI (M/.\ )= 1.85

TrEGOMe212 (3-7d).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 40H), 2.01, 3.21 (m, 1H), 3.29 (s, 3H), 3.50-

3.75 (br, 12H). 13C NMR (CDC13): 6 (ppm) 25.67, 29.96, 30.12, 30.12, 34.23, 59.24, 68.19,

70.74, 70.83, 70.85,70.88, 71.11, 72.18, 80.38. IR(v cm-1) 2923, 2853, 1464, 1350, 1115, 886,

721. GPC (THF vs. Polystyrene standards): M, = 117300; PDI (M .' ) = 1.55

TEGOMel5 (3-8a).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 29H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br,

16H). 13C NMR (CDC13): .6 (ppm) 27.08, 29.98, 30.37, 31.61, 38.37, 59.23, 70.59, 70.74, 70.81,

70.84, 72.16, 74.98. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs.

Polystyrene standards): M, = 117400 ; PDI (M/,.11 )= 1.50

TEGOMe21 (3-8b).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br,

16H). 13C NMR (CDC13): 6 (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 59.25, 70.61, 70.76, 70.83,

70.86, 72.18, 75.03. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs.

Polystyrene standards): M, = 146500 ; PDI (M/.1 ) = 1.25

TrEGOMel5 (3-8c).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 29H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br,

12H). 13C NMR (CDC13): .6 (ppm) 27.06, 29.96, 30.35, 31.59, 38.35, 59.22, 70.58, 70.74, 70.81,









70.84, 72.16, 74.97. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs.

Polystyrene standards): 1/,, = 42600 ; PDI (1, /f 1 = 1.71

TrEGOMe21 (3-8d).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br,

12H). 13C NMR (CDC13): 6 (ppm) 27.05, 29.96, 30.35, 31.57, 38.34, 59.23, 70.58, 70.75, 70.81,

70.85, 70.88, 72.17, 74.99. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs.

Polystyrene standards): 3f,, = 117300 ; PDI (- f,, 11, ) = 1.55

Results and Discussion

Synthesis and Structural Analysis

Figure 3-2 describes the synthesis of the ADMET amphiphiles used in this study.

Monomers 3-3a-d and 3-4a-d were prepared via Williamson etherification of primary and

secondary diene alcohols 3-la,b and 3-2a,b (synthsized as previously reported)13' 17 with

oligoethoxy-p-tosylates.59 The use of the primary diene alcohol places a carbon atom directly off

the backbone of the resulting polymer; throughout this report the monomers and polymers

produced in this fashion will be described as "primary." Using a secondary alcohol places an

oxygen atom directly off the backbone, monomers and polymer produced in this fashion will be

described as "secondary' throughout this report. Monomer structures were confirmed by 1H and

13C NMR, elemental analysis, and high resolution mass spectrometry. Polymerization with

Grubbs' 1st generation catalyst affords the unsaturated polymers 3-5a-d and 3-6a-d, which were

quantitatively hydrogenated with p-toluenesulfonyl hydrazide. Polymer structures were

confirmed by 1H and 13C NMR and FTIR. Molecular weights, (Table 3-1) were measured using

gel permeation chromatography (THF vs. polystyrene standards).









To simplify the discussion, a systematic nomenclature was adopted for these polymers and

monomers. Monomers are named with a prefix for the number of methylene carbons between the

PEG branch and the olefin (n in Figure 3-2), followed by the identity of the branch (TEGOMe

for tetra ethylene glycol (x = 4), methoxy terminated; TrEGOMe for tri ethylene glycol (x = 3),

methoxy terminated). Polymers are named first for the identity of the branch, followed by a

number indicating the frequency of the branch. Unsaturated polymers are denoted with the suffix

"u." Finally, monomers and polymers made from the secondary diene alcohols 3-la-b are given

the additional suffix "2." For example, monomers 3-3a and 3-4a are 6,6TEGOMe2 and

6,6TEGOMe, polymers 3-5a and 3-6a TEGOMe 5u2 and TEGOMel5u, polymers 3-7a and 3-8a

TEGOMel5 and TEGOMel52, respectively.

The slight structural differences between the primary and secondary monomers are

apparent in both the 1H and 13C NMR spectra. Figure 3-3 shows the 1H NMR spectra of

monomers 3-3a and 3-4a, chosen arbitrarily as examples. The signal at 3.28 ppm in the bottom

spectrum, corresponding to the methylene spacer, does not appear in the 3-3a spectrum. Also,

the resonance for the methine proton shifts from 1.54 ppm in the 3-4a spectrum to 3.22 ppm in

the 3-3a spectrum. The olefin and glycol region proton signals remain mostly unchanged

between the two monomers. The broad overlapping signal for the aliphatic protons emphasizes

the limitation of 1H NMR in the structural analysis of ADMET monomers and the need for

thorough 13C NMR analysis.

Figure 3-4 shows the 13C NMR spectra for monomers 3-3a and 3-4a. As in the proton

spectra, the 13C NMR spectra for the primary and secondary monomers show significant

differences. The position of the methine carbon shifts from 38.26 ppm in the spectrum of 3-4a to

80.27 in the spectrum of 3-3a. The resonance at 74.90 in the spectrum for 3-4a, absent in the









spectrum for 3-3a, corresponds to the methylene spacer carbon. The resonance at 68.22 in the

spectrum for 3-3a but absent in the spectrum of 3-4a corresponds to the first methylene carbon in

the glycol branch. The symmetric nature of the glycol branches results in the overlapping of the

remaining glycol carbon signals in both monomers (70.50-70.75 ppm), except for the methyl

endgroup carbon (59.16 ppm in both spectra) and the glycol carbon closest to the branch

terminus (72.15 ppm in both spectra, unlabeled in Figure 3-3).

Expansion of the aliphatic region (Figure 3-5) again reveals the effect of the slight

structural variation of the methylene spacer. Monomer 3-3a shows a strong downfield shift for

the methylene carbons adjacent to the central methine carbon when compared to 3-4a. There is

also an upfield shift for the next adjacent carbons in the spectrum for 3-3a compared to 3-4a, due

again to a difference in the magnetic environments of the two monomers' methine carbons.

However, past this the resonances are consistent for the remaining aliphatic carbons and the

allylic carbons.

The progression from monomer 3-4a to fully saturated polymer 3-8a (chosen as an

example), monitored by 1H and 13C NMR, is shown in Figure 3-6. Polymerization to 3-6a results

in the convergence of terminal olefin signals in the monomer spectra (4.89, 5.74 ppm in the 1H

spectrum, 114.26 and 139.31 ppm in the 13C spectrum) to a single internal olefin peak for the

unsaturated polymer (5.38 ppm in the 1H spectrum, 130.08 ppm in the 13C spectrum). Saturation

to form 3-8a results in the complete disappearance of any olefin signal in the spectra of the final

polymer. Coalescence of several individual backbone carbon peaks into a single peak, due to the

symmetric nature of the repeat unit, highlights the ability of ADMET chemistry to create pristine

polymer microstructures. The appearance of only the resonances predicted by the repeating unit

confirms the absence of side reactions or structural irregularities.









Typically, the quantitative hydrogenation of ADMET polymers is confirmed using FTIR

by the absence of the out-of-plane C-H wagging vibrational mode at 967 cm-1. This also occurs

with this family of polymers. However, a combination of NMR and IR is needed, because the

signal at 967 cm-1 is complicated by overlapping polyether stretches, which prevent baseline

resolution (Figure 3-7). However, the IR spectra serve to verify the absence of moisture in the

polymer films (no hydrogen bonding seen). This result helps confirm the interpretation of the

DSC data (discussed in the subsequent section), which indicate that the thermal behavior is due

to the bulk morphology of the polymer and is not a result of moisture content in the polyether

phase.

Thermal Analysis

Previous ADMET studies have shown that both melting temperature and melting enthalpy

decrease as the size of the pendant moieties increases.10 Interestingly, this trend is not observed

in the series of polymers described here. The tri ethylene glycol and tetra ethylene glycol grafts

show nearly identical peak melting temperatures and enthalpies when the branch distribution is

held constant (3-8a,c; 3-7a,c; 3-6b,d; 3-8b,d; 3-7b,d). This is compelling evidence that the model

presented above is correct, as the length of the graft doesn't alter the behavior of the crystallizing

backbone. Noticeable differences in glass transition between the tri ethylene glycol and tetra

ethylene glycol grafts support this model. Referring to Figure 3-8, which shows DSC plots for

polymers with tri ethylene glycol and tetra ethylene glycol grafts, in all cases the longer graft

results in a higher amorphous content and a more distinct glass transition.

There are also remarkable differences in the thermograms for the saturated and unsaturated

polymers. Comparing the melting temperatures in Table 3-2 for the unsaturated polymers to the

values for the saturated analogues (3-6b and 3-8b, 3-5b and 3-7b, 3-6d and 3-8d, 3-5d and 3-7d),

differences of more than 30 C are observed, but the Tg's remain essentially unchanged, an









indication that only the crystalline region (i.e., the PE backbone) is affected by the degree of

unsaturation and not the amorphous part. This once again supports our crystallization model: the

internal olefin acts a defect witch interrupts the all trans configuration of the methylene

sequences between branches, thus impeding crystallization.

The differences between in thermal response depending on the nature of the attachment of

the PEG branch (primary or secondary), and especially for the unsaturated polymers, further

support our model. The unsaturated primary polymers (Figure 3-8B) display rather complex

thermograms with multimodal melting profiles, while the secondary analogues (Figure 3-8A)

display a single melting peak characteristic of most ADMET polymers. The corresponding

saturated polymers show a difference between primary and secondary branch attachment, albeit

less significant. A decrease in melting enthalpy and a broadening of the endotherm is witnessed

for the secondary polymers, indicating a less perfectly formed crystal. This is definitive evidence

that the point of branching is affecting the folding of the chains and therefore the crystallization

and melting behavior.

The interesting melting behavior for TEGOMe21u (3-6b) and TrEGOMe21u (3-6d) were

further investigated using MDSC and selective annealing experiments. MDSC provide increased

sensitivity over conventional DSC, as well as the separation of kinetic and thermodynamic

components of the total heat flow. This allows for the resolution of weak or overlapping

transions.51,60-62 MDSC data (Figure 3-9A), confirmed the existence of two separate melting

endotherms in these unsaturatued polymers. During the dual annealing experiment we discovered

that the polymers could be conditioned thermally to prefer either of these two different

crystalline forms. The DSC thermograms obtained after annealing temperatures at -370C (just

below the higher temperature endotherm but above the lower temperature endotherm), at -57C









(just below the lower melting endotherm), and at -370C followed by -57C are shown in Figure

3-10B, (refer to Figure 3-8B for the unannealed curve).

Annealing at -370C results in a marked increase in the melting enthalpy for the higher

temperature transition compared to the unannealed polymer. The lower temperature peak

remains unaffected during this treatment. If the bimodal melt were the result of a melting and

recrystallization mechanism, the lower temperature endotherm would be suppressed by this

treatment, as crystallization would occur at temperatures above the melting point of these

crystallites. This is not the case. Similarly, annealing at -57C results in an increase in the

melting enthalpy of the lower temperature transition compared to the unannealed polymer, while

leaving the higher temperature transition unaffected. Annealing at both temperatures, first -37C

followed -57C produces two very sharp, distinct melting transitions. Further, the MDSC

experiment shows no crystallization occurring simultaneously along with melting, noted by the

absence of any exothermic transitions in any of the three heat flow signals. This confirms that the

bimodal melt must be due to different crystallite populations and not to a melting and concurrent

crystallization process. This again supports our current model of small, isolated crystallites.

The thermograms for the polymers with 15 carbons between the PEG grafts are shown in

Figure 3-10. When comparing the unsaturated polymers in Figure 3-10 to the unsaturated

polymers in Figure 3-8 (20 carbons between branch points), it becomes clear that the site of

unsaturation in the 15 family disrupts crystallization, resulting in completely amorphous

materials. The difference in the nature of the branch attachment (primary versus secondary) is

also witnessed in the 15 family, but the trend is opposite to that of the 21 family. The secondary

polymers (Figure 3-10A) exhibit a sharper, more defined melt with a greater melting enthalpy

compared to the primary polymers (Figure 3-10B). The peak melting temperature however, is









slightly depressed from the primary polymer, implying a thinner crystal. The reason for the

opposite trend for the 15 and 21 series is not clear at this point; however it is again evident that

the nature of the attachment of the PEG plays a crucial role in the crystallization of the backbone.

Despite the differences in the crystallinity, the behavior of the amorphous content for each

material is nearly identical for these polymers, the only exception being the tri ethylene glycol

grafted polymers, which exhibit a smaller ACp than the tetra ethylene glycol grafted polymers.

This is a clear indication that the amorphous regions across this entire family of polymers, which

remain unaffected with significant changes in the structure of the backbone and the observed

crystallinity, are primarily polyether. The DSC data for all of the polymers discussed is

summarized in Table 3-2 below.

The thermal stabilities are similar for all of the saturated polymers in this family. All are

stable up to 380 C, above which a single-stage, rapid decomposition is observed (Figure 3-11).

Conclusions

This chapter described the synthesis of a family of PEG grafted polyethylene amphiphilic

copolymers using ADMET chemistry. The graft length and graft distribution have been perfectly

controlled during the synthesis of the monomers. By altering several structural parameters we

have shown that the PEG branches are inducing folds in the backbone, resulting in small paraffin

like crystallites composed of the methylene sequences between branches. The site of

unsaturation in the backbone of the polymer plays an important role in the ability of the polymer

to crystallize. Likewise, the manner in which the PEG branch is connected to the backbone

changes the sterics and electronics as this fold point and alters the observed crystallinity. The

size of the PEG branch, however, does not affect this behavior significantly. These slight

variations in structure ultimately provide tunability over the properties of the final materials; the









melting point of the resulting materials can be controlled over a range of 60 C, or rendered fully

amorphous. Experiments involving PEG branches with different end groups, designed to induce

interactions of the branches within the amorphous phase of the polymer, are described in chapter

4.























= PEG branch

Figure 3-1: Model for chain folding and crystallization in ADMET amphiphiles.


"Secondary"
Monomers
and Polymers



"Primary"
Monomers
and Polymers


OH

n n
3-1

OH

n -2
3-2


x


3-3 ii


O O
x
n n
3-4


3-5 n
3-5 iii


3-6


o O


3-7

xO


3-8

n= 6, x= 4 (a)
n= 9, x= 4 (b)
n= 6, x= 3 (c)
n= 9, x= 3 (d)


Figure 3-2: ADMET amphiphile synthesis. i: NaH, DMF, TsO(CH2CH20)xCH3; ii: Grubbs' 1st
generation catalyst, 45 OC, vacuum; iii: TSH, TPA, o-xylenes 140 oC.
















G
E




B
A


Ap


ppm 6.0 5.0 4.0


Figure 3-3: H NMR spectra of monomers 3-3a and 3-4a.


3.0 2.0


1.0











monomer 3a


olefin


B

A
A


'I


PEG branch
endgroup
.I.


_ ~ ~ 1.~ _~~I I_~~~~___ ~ _~ -Y --


monomer 4a


A

B


ppm 125 100 75 50 25


Figure 3-4: 13C NMR for monomers 3-3a and 3-4a.










monomer 3a
F D B

A E C


A cD


0 monomer 4a
FDA

B E C
A C
A CD


I I I I
ppm 32.5 30.0 27.5 25.0

Figure 3-5: Assignment of aliphatic resonances in the 13C NMR spectra of monomers 3-3a and 3-
4a.



















terminal
olefin








internal
olefin

l .;! If A.n






no residual
olefin i


terminal
olefin










internal
olenn









no residual
olenn i


6o0 5.0 4.0 3.0 .0 1.0 ppm 150 100


Figure 3-6: Progression from monomer 4a to polymer 8a monitored by 1H and 13C NMR.


1000 SC0


v ({n-')


Figure 3-7: FTIR of TEGOMe21 and TEGOMe21u


75 54 25


4000 3500 3000 2500 2000 1500
v (cm"')


~~ ~''~~'~~''~~''"~`'' ''~'''''''










Secondary branch attachment, every 21st backbone carbon


C
o 1.0.
E


_6

4,
2 8






_2
IL
11


- TEGOMe Branch
----- TrEGOMe Branch


Unsaturated
Backbone

.-
SSaturated Backbone
50 -1DO -50
Temperature


0
(oC)


Primary branch attachment, every 21st backbone carbon
2.0 TEGOM
S -- TEGOMe Branch B
S----- TrEGOMe Branch
0
E 1.5




Unsaturated
Backbone

u. Saturated
t Backbone

-15D -100 -50 0 50
Temperature (C)

Figure 3-8: DSC comparison of secondary A) and primary B) polymers with PEG grafts every
21st backbone carbon.











MDSC: TEGOMe21u


NA


Total heat
flow



Reversing
heat flow


o


S-.




-

LL

I 0


D -100 -50 6
Temperature (C)


Annealing Experiments: TEGOMe21u and TrEGOMe21u
1.0
S TEGOMe21u B
------ TrEGOMe21u
-8

.6 --- :,,, -

S Anealed at-57_"C C


jAnealed aatt-C.
_ .4 .


S2
S Anealed at -37 "C,
then -57 "C
C n .


-150


-100 -50
Temperature (OC)


Figure 3-9: MDSC for TEGOMe21u A) and DSC annealing experiments for TEGOMe21u and
TrEGOMe21u B).


Nonreversing ----
heat flow


--/-V,\ \\I-











Secondary branch attachment, every 15th backbone carbon
1.2
C 1-2 A---------;----
TEGOMe Branch A
S --- TrEGOMe Branch
3 1.0i

8
U _

n Saturated
Backbone

LL Unsaturated /
-2 Backbone


-150 -100 50 0 50
Temperature (C)

Primary branch attachment, every 15th backbone carbon
1.0
-- TEGOMe Branch ,
----- TrEGOMe Branch ,
-8-
x
I x ---- V- ---
Lu Saturated
-2 ,Backbone .
-4-

o Unsaturated
Backbone
--------^----

-150 -100 -50 0 50
Temperature (oC)

Figure 3-10: DSC comparison of secondary A ) and primary B) polymers with PEG grafts every
15t backbone carbon.



















40
60'

40
20

100 200 300 400 500 600 700
Temperature (oC)

Figure 3-11: Thermo gravimetric analysis of saturated polymers (arbitrary vertical offsets for
clarity)









Table 3-1: Molecular weight data for polymers described in chapter 3
Polymer Ma (kg/mol) 3 ,, a (kg/mol) PDIb
TEGOMel5u (3-6a) 62.7 100.4 1.60
TrEGOMe 5u (3-6c) 21.4 37.2 1.74
TEGOMel5u2 (3-5a) 50.7 88.7 1.75
TrEGOMel5u2 (3-5c) 42.9 79.5 1.85
TEGOMel5 (3-8a) 78.1 117.4 1.5
TrEGOMel5 (3-8c) 24.9 42.6 1.71
TEGOMel52 (3-7a) 53.9 92.2 1.71
TrEGOMel52 (3-7c) 46.8 86.7 1.85
TEGOMe21u (3-6b) 54.8 96.2 1.76
TrEGOMe21u (3-6d) 33.5 57.7 1.72
TEGOMe21u2 (3-5b) 64.1 114.5 1.78
TrEGOMe21u2 (3-5d) 64.1 108.7 1.69
TEGOMe21 (3-8b) 117.2 146.5 1.25
TrEGOMe21 (3-8d) 41.1 70.3 1.71
TEGOMe212 (3-7b) 87.9 127.5 1.44
TrEGOMe212 (3-7d) 75.6 117.3 1.55
" GPC vs. polystyrene standards; b 1. I


Table 3-2: DSC data for polymers described in chapter 3
Polymer Tg (C) AC, (J/g-C) T, (oC) AH (J/g) Tc (oC) AH, (J/g)
TEGOMel5u (3-6a) -80 1.0 n/a n/a n/a n/a
TrEGOMe15u (3-6c) -81 1.0 n/a n/a n/a n/a
TEGOMe15u2 (3-5a) -81 1.0 n/a n/a n/a n/a
TrEGOMel5u2 (3-5c) -81 0.9 n/a n/a n/a n/a
TEGOMel5 (3-8a) -76 0.5 -9 21 -36 27
TrEGOMel5 (3-8c) -70 0.2 -6 24 -36 32
TEGOMel52 (3-7a) -76 0.4 -19 31 -28 31
TrEGOMel52 (3-7c) -74 0.3 -18 40 -29 38
TEGOMe21u (3-6b) -76 0.3 -38 18 -46 17
TrEGOMe21u (3-6d) -76 0.3 -41 22 -49 23
TEGOMe21u2 (3-5b) -76 0.4 -21 21 -37 22
TrEGOMe21u2 (3-5d) -70 0.3 -20 20 -36 22
TEGOMe21 (3-8b) -74 0.4 15 44 7 43
TrEGOMe21 (3-8d) -74 0.2 14 45 8 45
TEGOMe212 (3-7b) -71 0.3 12 45 -1 45
TrEGOMe212 (3-7d) -65 0.2 13 50 -1 50









CHAPTER 4
INDUCING PENDANT BRANCH SELF ASSEMBLY IN ADMET AMPHIPHILES

Introduction

It is well understood that highly regular macromolecular structures result in predictable and

controllable behavior. This is especially true with amphiphilic copolymers, for which minor

alterations in structure can induce a broad range of responses in the bulk and in solution.63-67 The

amount of research on the synthesis and self assembly of amphiphilic block copolymers alone is

remarkable.35 37,41'46,67-69 Living radical,3770 cationic,36,41 anionic,71 and even metathesis72

polymerizations have been extensively utilized in creating well defined structures that can self

assemble to form interesting and useful morphologies.

The use of acyclic diene metathesis (ADMET) to create highly regular, precisely defined

structures is also well known.9-11 These materials, while often structurally related to copolymers

made via chain copolymerization of ethylene and vinyl comonomers, possess properties that set

them apart as a completely separate class of materials.9' 12-14, 16-19, 28, 31, 53 These properties are

highly tunable with minor structural alterations, imparted during the synthesis of the symmetrical

terminal diolefin monomer. Two parameters are generally altered: the identity of the pendant

functional moiety and the static methylene sequence length between this functional group and

the terminal olefin. When the pendant moiety is a methyl group, systematically changing the

methylene sequence length from branches every 7th carbon to branches every 21st carbon results

in a control of melting point over a range of 200 oC.19 24 Likewise, alteration of the pendant

group size and polarity allow tunability of the properties when the methylene sequence length is

held constant. In all ADMET copolymers observed previously, an increase in defect size results

in a systematic decrease in melting temperature.13 14, 18









The previous chapters described the use of ADMET to synthesize a family of amphiphilic

graft copolymers with polyethylene (PE) backbones and hydrophilic polyethylene glycol (PEG)

branches. By combining the structural regularity available with ADMET and the ability of

amphiphiles to phase separate and self assemble we have created semicrystalline materials in

which the PE backbone crystallizes, forming pure hydrocarbon crystallites excluding the

polyether branches.15 This chapter describes the expansion of this area of research by altering the

pendant PEG chain end group to create copolymers with PE backbones and AB amphiphilic

grafts. Two of the polymers reported have the A-g-(B-b-A) motif, where an oligoethylene chain

is affixed to the end of the PEG branch directly attached to the PE backbone. The third has a

pyrene group attached to the end of the PEG chain. Labeling in the fashion allows the

aggregation of these graft end groups to be examined using fluorescence measurements. To

assess the influence of these pendant groups on the PE backbone accurately, the distance

between pendant groups was kept constant in this chapter. A 21-carbon distance between

pendant branches was chosen to ensure the crystallization of the backbone because previous

ADMET polymers with this functional group distribution have always been semicrystalline.9-11

All monomer and precursor structures were confirmed by 1H and 13C NMR, elemental

analysis and high resolution mass spectrometry. The structures of the corresponding polymers

were confirmed by 1H and 13C NMR, and FTIR. Differential Scanning Calorimetry (DSC) and

temperature modulated DSC (MDSC) were used to study the behavior of these materials in the

bulk. The observed thermal behavior indicates that the three materials have very different

morphologies. Affixing the PEG branch with a pyrene end group results in the complete

exclusion of the pendant moiety from the crystal, simultaneously inducing their aggregation.

Changing the end group to an n-hexyl chain results in crystallization of the pendant branch









separately from the PE backbone. Extending this olgioethylene chain from n-hexyl to n-

tetradecyl allows the pendant moiety to extend back into the polymer crystal, thereby increasing

the melting point compared to the polymer with the 6-carbon terminus. The inclusion of the

tetradecyl group into the crystal and resultant increase in melting point compared to the other

materials presented here is significant because it breaks the usual trend for ADMET polymers,

which show a decrease in melting point and melting enthalpy with increasing pendant group size.

Experimental Section

Instrumentation

All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian

Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to

residual signals from CDC13 (1H: 6= 7.27 ppm and 13C: 6 = 77.23 ppm) with 0.03% v/v TMS as

an internal reference. Thin layer chromatography (TLC) was performed on EMD silica gel

coated (250 ptm thickness) glass plates. Developed TLC plates were stained with iodine

adsorbed on silica to produce a visible signature. Reaction conversions and relative purity of

crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR)

measurements were conducted with a Bruker Vector 22 Infrared Spectrophotometer using

polymer films cast from chloroform onto KBr plates using High resolution mass spectrometry

analyses were performed on a Bruker APEX II 4.7 T Fourier Transform Ion Cyclotron

Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization

(ESI). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA).

Molecular weights and molecular weight distributions (Mw\ ) were determined by gel

permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid

chromatography system with an internal differential refractive index detector (DRI) and two









Waters Styragel HR-5E columns (10 micron particle diameter, 7.8 mm ID, 300 mm length) at 40

C. The mobile phase was HPLC grade tetrahydrofuran at a flow rate of 1.0 mL/minute).

Retention times were calibrated versus polystyrene standards (Polymer Laboratories; Amherst,

MA).

Differential scanning calorimetry (DSC) and temperature modulated differential scanning

calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid

nitrogen cooling accessory calibrated using sapphire and high purity indium metal. All samples

were prepared in hermetically sealed pans (4-7 mg/sample) and were referenced to an empty pan.

Samples were run under s purge of helium gas. A scan rate of 10 C per minute was used unless

otherwise specified. Modulated experiments were scanned with a 3 OC per minute linear heating

rate with modulation amplitude of .45 C and period of 30 seconds. Melting temperatures are

taken as the peak of the melting transition, glass transition temperatures as the mid point of a step

change in heat capacity.

Materials

Unless otherwise stated, all reagents were purchased from Aldrich and used without further

purification. Grubbs' 1st generation catalyst was a gift from Materia, Inc. Diene alcohol 4-1 was

synthesized as previously reported.17

Synthesis of 2-(10-undecenyl)-12-tridecenyl-l-tetra(ethylene glycol)-p-tosylate (4-2).

Anhydrous DMF (30 mL) was cannula transferred into an oven dried, 3-neck round-

bottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents

of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and 1

equivalent of 4-1 in 20 mL of anhydrous DMF was added via syringe. When hydrogen gas

evolution (monitored by bubbler) ceased, the solution was cannula transferred into a well-stirred

flask containing 4.5 equivalents of tetraethylene glycol di-p-tosylate in 50 mL of anhydrous









DMF. The reaction was stirred for 17 hours at 0 OC and quenched by pouring into 300 mL of

water. The resulting mixture was extracted with diethyl ether and the combined organic washed

with brine. Concentration afforded a yellow oil which was further purified by column

chromatography, 30% ethyl acetate 70% hexane eluent, yielding 1.5g (52%) of colorless oil. 1H

NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 2.42 (s, 3H), 3.29 (d, 2H), 3.50-3.75

(br, 15H), 4.18 (d, 2H), 4.98 (m, 4H), 5.82 (m, 2H), 7.31 (d, 2H), 7.79 (d, 2H). 13C NMR

(CDC13): 6 (ppm) 21.82, 27.01, 29.15, 29.35, 29.70, 20.80, 29.83, 30.28, 31.55, 34.00, 38.32,

68.89, 69.39, 70.57, 70.74, 70.79, 70.80, 70.88, 70.97, 75.01, 114.28, 128.18, 129.99, 133.33,

139.43, 144.92. ESI/HRMS: [M+NH4]+ calcd for NH4C39H6807S, 698.5024; found 698.5023.

Anal. (CH) calcd for C39H6807S: C, 68.78; H, 10.06. Found C, 58.51; H, 9.95.

General Procedure for Preparation of Monomers

Anhydrous DMF (45 mL) was cannula transferred into an oven dried, 3-neck round-

bottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents

of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and 3 was

added in 20 mL of anhydrous DMF via syringe. When hydrogen gas evolution (monitored by

bubbler) ceased, 1 equivalent of 4-2 in 30 mL of anhydrous DMF was added via syringe. The

reaction was stirred for 17 hours at 0 OC and quenched by pouring into 300 mL of water. The

resulting mixture was extracted with diethyl ether and the combined organic washed with brine.

Concentration afforded a yellow oil which was further purified by column chromatography.

2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) methenyl pyrene (9,9TEGOPy, 4-
3a).

Column Chromatography:30% ethyl acetate 70% hexane eluent afforded .475g (29%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H),

3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.28 (s, 2H), 5.82 (m, 2H), 7.61-8.79 (m, 4H), 8.13-8.20 (m,









4H), 8.37 (d, 1H). 13C NMR (CDC13): 6 (ppm) 26.96, 29.14, 29.35, 29.71, 20.82, 29.85, 30.28,

31.52, 34.01, 38.28, 69.72, 70.54, 70.75, 70.83, 70.87, 70.95, 72.04, 74.96, 114.28, 123.75,

124.64, 124.92, 125.36, 126.09, 127.22, 127.60, 127.83, 131.03, 131.47, 131.62, 139.43.

ESI/HRMS: [M+NH4]+ calcd for NH4C49H7205, 758.5718; found 758.5735. Anal. (CH) calcd

for C49H7205: C, 79.41; H, 9.79. Found C, 79.00; H, 9.80.

2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) mono n-hexyl ether (9,9TEGOHex,
4-3b).

Column Chromatography: 20% ethyl acetate 80% hexane eluent afforded .144g (17%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 41H), 2.01 (q, 4H),

3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): 6

(ppm) 14.21, 22.78, 25.95, 26.92, 29.12, 29.33, 29.68, 29.79, 29.82, 30.26, 31.53, 31.87, 33.98,

38.31, 70.26, 70.57, 70.78, 70.81, 70.83, 71.71, 74.98, 114.25, 139.33. ESI/HRMS: [M+NH4]+

calcd for NH4C38H7405, 628.5875; found 628.5887. Anal. (CH) calcd for C38H7405: C, 74.70; H,

12.21. Found C, 74.84; H, 12.36.

2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) mono n-tetradecyl ether
(99TEGOC14, 4-3c).

Column Chromatography: 20% ethyl acetate 80% hexane eluent afforded .400g (34%

yield) of colorless oil. 1HNMR (CDC13): 6 (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 57H), 2.01 (q, 4H),

3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDC13): 6

(ppm) 14.29, 22.88, 26.31, 27.03, 29.16, 29.36, 29.55, 29.71, 29.82, 29.85, 29.87, 30.29, 31.57,

32.13, 34.01, 38.35, 70.29, 70.60, 70.79, 70.84, 70.86, 71.75, 75.01, 114.27, 139.40. ESI/HRMS:

[M+NH4]+ calcd for NH4C38H7405, 628.5875; found 628.5887. Anal. (CH) calcd for C38H7405:

C, 74.70; H, 12.21. Found C, 74.84; H, 12.36.









General Procedure for ADMET Polymerizations

Monomers were dried under vacuum at 80 OC for 48 hours prior to polymerization and

subsequently transferred to a 50 mL round-bottom flask equipped with a magnetic stir bar.

Grubbs 1st generation catalyst (300:1 monomer:catalyst ratio) was added and the flask was

stirred under vacuum at 45 C for 4 days. Polymerizations were quenched with ethyl vinyl ether

(5 drops in degassed toluene), precipitated into cold, acidic methanol to remove catalyst residue,

and isolated as adhesive gums.

Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) methenyl pyrene
(TEGOPy21u, 4-4a).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.50-3.75 (br,

12H), 5.28 (s, 2H), 5.35 (m, 2H), 7.61-8.79 (m, 4H), 8.13-8.20 (m, 4H), 8.37 (d, 1H). 13C NMR

(CDC13): 6 (ppm) 27.05, 27.46, 29.46, 29.35, 29.59, 29.78, 29.92, 30.02, 30.35, 31.57, 32.86,

38.33, 69.73, 70.54, 70.76, 70.83, 70.87, 70.95, 72.05, 74.96, 123.75, 124.64, 124.93, 125.13,,

125.33, 125.38, 126.10, 127.23, 127.57, 127.60, 127.84, 129.60, 130.08 (cis olefin), 130.53

(trans olefin), 131.03, 131.44, 131.47, 131.62. IR (v cm-1) 2923, 2853, 1464, 1350, 1260, 1115,

967, 846, 802, 721. GPC (THF vs. Polystyrene standards): M, = 80300 ; PDI (M/. \ ) = 1.90

Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) mono n-hexyl
ether (TEGOHex21u, 4-4b).

H NMR (CDC13): 6 (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 41H), 2.01 (q, 4H), 3.29 (d, 2H),

3.41 (t, 2H), 3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 14.26, 22.83, 25.99,

27.08, 29.49, 29.83, 29.97, 30.36, 31.61, 31.91, 32.87, 38.38, 70.29, 70.60, 70.86, 71.63, 75.06,

130.09(cis olefin), 130.55 (trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 967,

846, 802, 721. GPC (THF vs. Polystyrene standards): 3f,, = 84800 ; PDI ( 1,, /., ) = 1.98









Polymerization of 2-(10-undecenyl)-12-tridecenyl-l-tetra (ethylene glycol) mono n-
tetradecyl ether (TEGOC1421u, 4-4c).

1HNMR (CDC13): 6 (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 57H), 2.01 (q, 4H), 3.29 (d, 2H),

3.41 (t, 2H), 3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 14.29, 22.88, 26.31,

27.03, 29.16, 29.36, 29.55, 29.71, 29.82, 29.85, 29.87, 30.29, 31.57, 32.13, 34.01, 38.35, 70.29,

70.61, 70.79, 70.84, 70.86, 71.76, 75.01, 130.08 (trans olefin), 130.54 (trans olefin). IR (v cm-1)

2923, 2853, 1464, 1350, 1260, 1115, 967, 846, 802, 721. GPC (THF vs. Polystyrene standards):

3f,, = 61900 ; PDI (I f,, 1, ) = 1.71

General Procedure for the Hydrogenation of Unsaturated Polymers

Unsaturated polymers were dissolved in dry o-xylene. P-toluenesulfonyl hydrazide (TSH)

and tripropyl amine (TPA) were added with stirring (3 equiv each). The resulting solution was

refluxed for 3-4 hours while monitoring nitrogen evolution with a bubbler. When gas evolution

ceased, the solution was cooled to room temperature, an additional 3 equivalents of TSH and

TPA were added, and the solution was refluxed for another 3 hours. The solutions were then

concentrated to one-half of the original volume and precipitated into cold, acidic methanol. The

polymers were isolated as elastic, adhesive gums.

TEGOPy21, (4-5a).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.50-3.75 (br, 12H), 5.28 (s,

2H), 7.61-8.79 (m, 4H), 8.13-8.20 (m, 4H), 8.37 (d, 1H). 13C NMR (CDC13): 6 (ppm) 27.05,

29.96, 30.02, 30.35, 31.59, 38.34, 69.76, 70.56, 70.78, 70.85, 70.87, 70.97, 72.05, 74.97, 123.75,

124.64, 124.95, 125.15,, 125.33, 125.38, 126.10, 127.23, 127.57, 127.61, 127.84, 129.60,

131.05, 131.44, 131.48, 131.66. IR (v cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 846, 802, 721.

GPC (THF vs. Polystyrene standards): M, = 60400 ; PDI (M/\ ) = 1.93









TEGOHex21 (4-5b).

1HNMR (CDC13): 6 (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 49H), 3.29 (d, 2H), 3.41 (t, 2H),

3.50-3.71 (br, 16H). 13C NMR (CDC13): 6 (ppm) 14.28, 22.85, 25.99, 27.07, 29.83, 29.97, 30.38,

31.58, 31.93, 38.35, 70.29, 70.60, 70.84, 70.86, 71.77, 75.02. IR (v cm-1) 2923, 2853, 1464,

1350, 1260, 1115, 846, 802, 721. GPC (THF vs. Polystyrene standards): M, = 79200 ; PDI

(Mw/.1 )= 1.78

TEGOC1421 (4-5c).

1H NMR (CDC13): 6 (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 65H), 3.29 (d, 2H), 3.41 (t, 2H),

3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 14.29, 22.88, 26.31, 27.03, 29.55,

29.71, 29.82, 29.87, 29.97, 30.35, 31.60, 32.13, 38.38, 70.28, 70.61, 70.86, 71.76, 75.01. IR (v

cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 846, 802, 721. GPC (THF vs. Polystyrene

standards): M, = 65800; PDI (M.\ 1 ) = 1.76

Results and Discussion

Synthesis and Structural Analysis

Figure 4-1 describes the synthesis of these unique materials. First, diene alcohol 4-1

(prepared as previously described17) is attached to the PEG branch via Williamson etherification

with tetra(ethylene glycol)di p-tosylate. Disubstitution is avoided using careful stoichiometry.

The hydrophobic endgroup is then attached to 4-2 with a second Williamson by using the

appropriate alcohol. This synthetic method is general and can potentially be applied to prepare an

array of ADMET monomers and subsequent polymers having a variety of functional groups

separated from the PE backbone by a PEG spacer. Monomers 4-3a-c are polymerized in the bulk

at 45 C under high vacuum using Grubbs' first generation catalyst to afford the unsaturated









ADMET polymers 4-4a-c. Subsequent hydrogenation with p-toluenesulfonyl hydrazide results in

the final fully saturated polymers 4-5a-c.

For simplicity, a systematic nomenclature has been adopted for these monomers and

polymers. Monomers are given the prefix "9,9" to indicate the number of methylene carbons

between the branch and the olefin, followed by the identity of the pendant group (TEGO for tetra

ethylene glycol and either Py, Hex, or C14 for pyrene, n-hexyl or n-tetradecyl). Polymers are

named first for the identity of the pendant defect, followed by the branch frequency. Unsaturated

polymers are denoted with the suffix "u." For example, monomer 4-3a is named "9,9TEGOPy,"

polymer 4-4a "TEGOPy21u," and polymer 4-5a "TEGOPy21."

The 1H and 13C NMR spectra for 9,9TEGOTs (4-2) are shown in Figure 4-2. In the proton

spectrum the tosyl end group is clearly identified by the two doublets at 7.32 and 7.72 ppm, as

well as the singlet at 2.45 ppm. The triplet at 4.16 ppm corresponds to the methylene protons

adjacent to the tosyl group, shifted downfield from the overlapping glycol proton signals which

appear from 3.55 to 3.61 ppm. The doublet at 3.30 ppm corresponds to the methylene protons

separating the glycol moiety from the backbone. The allylic protons display a quartet at 2.03

ppm, the central methine carbon shows a multiple at 1.56 ppm, and the characteristic terminal

olefin peaks are seen at 4.91 and 5.80 ppm. Finally, the remaining methylene protons of the

diene main chain overlap into a single broad peak at 1.26 ppm. In the carbon spectra for

99TEGOTs the resonances for the tosyl group are seen at 144.92, 133.33, 129.99, 128.18 ppm

(aromatic carbons) and 21.83 ppm (methyl carbon). Terminal olefin signals appear at 114.28 and

139.43 ppm, the methylene carbon connecting the branch to the backbone appears at 75.01 ppm,

and the glycol carbons overlap from 70.58 to 70.97 ppm. The glycol carbons closest to the tosyl

group appear at 68.90 ppm, the central methine carbon is at 38.32 ppm, and the allylic carbons









are at 34.01 ppm. The remaining resonances for the internal methylene carbons appear from 27

to 32 ppm and are all individually resolved. This highlights the need for thorough 13C analysis in

the ADIMET synthesis of precise polyolefins, because simply investigating the 1H spectra can

lead to ambiguities due to overlapping resonances.

The 1H and 13C NMR spectra of 9,9TEGOPy (4-3a) are shown in Figure 4-3. In the proton

spectrum the aromatic pyrene protons appear from 8.02 to 8.43 ppm. The methylene protons

between the pyrene and glycol branch appear as a singlet at 5.30 ppm. The resonances for the

glycol region, terminal olefin, allylic, and aliphatic protons remain mostly unchanged compared

to the 1H spectrum of 9,9TEGOTs. The case is similar for the carbon spectrum of 9,9TEGOPy.

The aromatic pyrene carbons appear from 123.74 to 131.61 ppm, and the methylene carbon

between the pyrene and glycol moieties is seen at 72.04 ppm. As in the proton spectrum, the

terminal olefin, allylic, and aliphatic carbons remain mostly unchanged compared to the carbon

spectrum of 9,9TEGOTs.

Figures 4-4 and 4-5 show the 1H and 13C NMR spectra of 9,9TEGOHex (4-3b) and

9,9TEGOC14 (4-3c), respectively. In the proton spectra the n-hexyl and n-tetradecyl methyl end

groups appear at 0.87 ppm, and the methylene protons adjacent to the glycol portion of the

branch appear as triplets at 3.44 ppm. The rest of the n-hexyl protons overlap with the internal

methylene protons of the diene main chain. The remaining resonances are unchanged as

described in the previous example. The carbon spectra for these monomers are nearly identical

except for the aliphatic regions, which are complicated by the overlapping diene main chain and

aliphatic branch carbon resonances.

An expanded view of the aliphatic regions in the 13C NMR spectra of 9,9TEGOHex,

9,9TEGOC14, and 9,9TEGOPy is shown in Figure 4-6. Comparing 9,9TEGOPy to the two









monomers with aliphatic branch end groups allows the resonances for the diene main chain to be

separated from the aliphatic end group resonances. Still, particularly in the case of 9,9TEGOC14,

the number of overlapping resonances greatly complicates the interpretation of this region.

The progression from diene monomer through unsaturated polymer, to saturated polymer

(monitored by 1H and 13C NMR) is shown in Figure 4-7 for 9,9TEGOC14 (4-3c) through

TEGOC1421 (4-5c) (arbitrarily chosen as an example). Polymerization to 4-4c results in

convergence of the terminal olefin signals in the monomer spectrum to a single peak for internal

olefin seen in both the 1H and 13C spectra. Hydrogenation results in the complete elimination of

any olefin signal in either the proton or the carbon spectra. The appearance of only the

resonances predicted by the fundamental repeat unit confirm the absence of side reactions and

structural irregularities, again highlighting the effectiveness of ADMET chemistry in the

synthesis of pristine, highly regular polymer structures. Molecular weight data (GPC in THF vs.

polystyrene standards) are displayed in Table 4-1.

Thermal Analysis

The DSC data for the new polymers are presented in Table 4-2. The polymers exhibit

remarkably different thermal behavior, a clear indication that changing the graft end group

moiety has significant effects on the morphology of these systems. The difference in behavior

between the saturated and unsaturated polymers is also significant, emphasizing the role of the

PE backbone on the crystallization in these materials.

The DSC profiles for TEGOPy21 and TEGOPy21u are shown in Figure 4-8. The heating

and cooling curves show that the saturation of the backbone allows for crystallization to occur,

while the unsaturated polymer remains completely amorphous. This is clear evidence that the

pendant defect is not involved in the crystallization and therefore must be excluded from the

crystal. The Tg of the saturated polymer is also slightly increased compared to the unsaturated









analogue, an indication that segmented motion of the grafts is restricted by the crystallinity. The

completely amorphous behavior of TEGOPy21u is an interesting result, considering that

previous reported unsaturated ADMET polymers with the same distribution of pendant

functionality are semi crystalline.9-11 The lack of crystallinity in TEGOPy21u, as well as the

significantly depressed melting point for the saturated analogue compared to our previous

ADMET amphiphilic copolymers15 is a result of pyrene aggregation impeding segmental motion

as well as backbone crystallization. This is confirmed by pyrene excimer formation seen in the

fluorescence spectra for both the unsaturated and saturated polymers (Figure 4-9).

The DSC curves for TEGOHex21 and TEGOHex21u are shown in Figure 4-10. The

difference in behavior between the saturated and unsaturated polymers is especially interesting in

this pair. The unsaturated polymer is semicrystalline with a melting endotherm at -13 OC. There

is significant amorphous content to this material as well, indicated by the distinct Tg at -76 oC.

The heating and cooling profiles are typical for unsaturated ADMET polymers. The thermal

behavior of the saturated analogue is completely different, however. A single, bimodal

crystallization at -40C is witnessed on cooling. Upon heating a small exotherm is barely observed

at -91 OC, followed by a bimodal melting endotherm with peaks at -48 OC and -37 oC. A second

bimodal melting endotherm occurs with peaks at 4 OC and 11 C.

The complex behavior of TEGOHex21 was further investigated by MDSC, which provides

increased sensitivity compared to traditional DSC and allows for resolution of overlapping

transitions.51 60-62 The MDSC heating traces are shown in Figure 4-11. In the nonreversing and

total heat flow signals the cold crystallization event, barely perceptible in Figure 4-10, is clearly

visible. This is followed by the first bimodal melting endotherm, which is observed in all three

signals. In the nonreversing signal this transition is first exothermic, then endothermic, indicating









that the bimodal melt is actually the result of a melting and concurrent crystallization

mechanism.60 The same is true for the higher temperature bimodal endotherm; clear exothermic

activity in both the total and nonreversing signals indicates melting and simultaneous

crystallization. Because the melting enthalpy of this higher temperature peak (21 J/g) matches

the enthalpy of crystallization (21 J/g), and also because its metling temperature and enthalpy

(4C and 27 J/g) are in good agreement with those of TEGOPy21 (90C and 24 J/g), it can be

concluded that this behavior is a result of crystallization of the backbone excluding the pendant

branch. The backbone crystallizes during cooling. Then during subsequent heating, the excluded

branches gain sufficient mobility to self crystallize, noted by the exotherm at -1000C. The

pendant crystals then melt at about -50C, followed by the melting of the backbone crystals.

The thermal behavior of TEGOC1421u and TEGOC1421 (Figure 4-12) differs significantly

from the previous two examples. Both polymers exhibit extremely sharp melting transitions at

temperatures much higher than the other polymers in this family. This deviates from the well

known trend for ADMET polymers, which show a decrease in Tm and AHm as the defect size

increases. For TEGOC1421u and TEGOC1421, the increase in pendant group length results in

marked increases in both melting temperature and enthalpy. Further, no Tg is observed in either

the saturated or unsaturated analogues, indicating greatly reduced amorphous content for these

polymers. Thus, the long alkyl chains must also be crystallizing. Since there is only one melting

peak the C14 chain must be long enough to extend back into the crystallizing PE backbone,

forming a single crystallized region.

Conclusions

The synthesis of polyethylene with precise placement of amphiphilic grafts has been

achieved. These polymers feature PEG grafts attached to the polyolefin backbone with different

hydrophobic groups affixed to the end of the PEG chains. These structural differences induce









significant changes in the thermal behavior of the corresponding materials. When the graft end

group is a pyrene moiety, the polyolefin backbone crystallizes excluding the pendant branch.

When the end group is changed to an n-hexyl chain, the branches and the backbone crystallize

separately, forming two different crystalline regions. Extending this end group from an n-hexyl

to an n-tetradecyl chain allows the branches and backbone to crystallize together, resulting in the

inclusion of the branch within the PE crystal. This material breaks the well known trend for

ADMET polymers, which show a decrease in T, and AH, as the defect size increases. Most

importantly we have demonstrated that a pendant group can be intentionally excluded from the

crystallized polyethylene backbone and induced to self interact. This displays the promise such

architectures could have in advanced applications such as membrane technologies or polymer

electrolytes.









OH OTs

99 9 9
4-1 4-2


OOR OIOi
n 4 iv9 n 4
99 9 9


iiOR

9 9


4-3


a -1

R= b "1
C -1


Figure 4-1: Synthesis of polyethylene with precisely placed amphiphilic branches. i: NaH,
tetra(ethylene glycol)di-p-tosylate, DMF; ii: NaH, ROH, DMF; iii: Grubbs' 1st
generation catalyst, 45 C, vacuum; iv: TSH, TPA, o-xylene, 140 C.


iii


















Sk
Hj f
h


a b d e 9 i
I I ^ IA


PPM 8-D 7.0

h


60 5.0 4.0
---- -- m


3.0 2. 1I0
3.0 20 1.0


de f


Sii

r m owr .. ........ 11


ppm


Figure 4-2 and 3C NMR spectra of 9,9TEGOTs (4-2).
Figure 4-2: H and 13C NMR spectra of 9,9TEGOTs (4-2).


























ppm 8.0 7.0 60 50 4.0 3.0 2.0 1.0


0-
do Oe
c3 g

b


el h






150 100 50 ppm

Figure 4-3: 1H and 13C NMR spectra of 9,9TEGOPy (4-3a).











h
_ -


3 a

f b
h


a.e.g. .


ppm 80 710 60 5.0 40D

e e
k

h 3 d f---j



b


3.0 2.0 1.0


I'- .Z -lT- -- l r--2"ImI I. I 2Z2 Z2 l -. -- -


150 100 50

Figure 4-4: H and 13C NMR spectra of 9,9TEGOHex (4-3b).


ppm


C


i













C C
ed

3 a
f b

h
H


df
a _
A


ppm 8.0 7.0

e


6.0 50D 4.0 3.0 2.0 1.0
i
f J
k
d i 12
d e




h


ppm


150 100 50

Figure 4-5: H and 13C NMR spectra of 9,9TEGOC14 (4-3c).


uru----- --~,r..ru-i~hu~.....rluuuu~ui.~~an~ I~uurru~ ~ll~l~l~lk












O-Pyrene
i 9 d h
b c f e a
de
a f h

b












b c
b a

.9







C
a
8










c a


----Lu
0b bd b,*

-9














ppm34.0 33.0 320 31.0 30.0 29.0 28.0 27.0 26.0



Figure 4-6: Expansion of the aliphatic regions of the 13C spectra of 9,9TEGOPy, 9,9TEGOHex,
and 9,9TEGOC14 (3a-c).













terminal
o efin


internal
olefin


no residual
olefin __


terminal
olefin






internal
otefin







no residual
olefln


6.0 5.0 410 3-0 2.0 1.0 ppm 100 50
Figure 4-7: Progression from monomer 4-3c to saturated polymer 4-5c monitored by NMR.


L_


.%I hI


























-1.0
-1!


Temperature (oC)


Figure 4-8: DSC heating and cooling traces for TEGOPy21u (4-4a) and TEGOPy21 (4-5a).






to1 A A 1oA

0.8- 0.8

N06 0- o.6
0-4- < 0.4

0.2- 0.2-

0.0- 0.0
300 400 500 600 700 300 400 500 600


Wavelength (nm)


Wavelength (nm)


Figure 4-9: Absorption and fluorescence spectra for TEGOPy21 A) and TEGOPy21u B)


























-1.0
-150


Temperature (oC)


Figure 4-10: DSC heating and cooling traces for TEGOHex21u (4-4b) and TEGOHex21 (4-5b).

5-



0 _4- reversing heat
E fl11

3-




nonreversing heat flow
/11


0
-150 -100 -50 0 50
Temperature (oC)
Figure 4-11: MDSC heating traces for TEGOHex21 (4-5b).







123










3.0
3 -- Saturated
S ----- Unsaturated r

E 1.5 I
Ii i

--- -
L 0
^ i """ *"*-- --- _- -- -------- ------------




S-3

-100 -75 -50 -25 0 25 50
Temperature (oC)


Figure 4-12: DSC heating and cooling traces for TEGOC1421u (4-4c) and TEGOC1421 (4-5c).































124









Table 4-1: Molecular weight data for polymers described in chapter 4.
Polymer Ma (kg/mol) 3 ,, a (kg/mol) PDIb
TEGOPy21u (4a) 42.2 80.3 1.9
TEGOPy21 (5a) 31.2 60.4 1.93
TEGOHex21u (4b) 42.8 84.8 1.98
TEGOHex21 (5b) 44.4 79.2 1.78
TEGOC1421u (4c) 36.2 61.9 1.71
TEGOC1421 (5c) 37.3 65.8 1.76
a GPC vs. polystyrene standards; b' 1f, i



Table 4-2: DSC data for polymers described in chapter 4.
Polymer Tg (OC) ACp (J/g-C) T, (OC) AH, (J/g) Tc (OC) AH, (J/g)


TEGOPy21u -36 0.76 n/a
TEGOPy21 -21 0.36 9
TEGOHex21u -76 0.49 -13
TEGOHex21 n/a n/a -37, 4
TEGOC1421u n/a n/a -3
TEGOC1421 n/a n/a 23


n/a
24
21
8, 27
50
71


n/a
-12
-54
-4
-7
17


n/a
25
21
28
51
72









CHAPTER 5
SYNTHESIS OF DEUTERIUM LABELED ADMET AMPHIPHILES

Introduction

This dissertation explores the effects that altering various parameters have on the overall

response in a family of materials with related structures. Chapter 2 outlines the basics of this

study where altering the distribution of the hydrophilic branch as well as the identity of the

branch end group could affect the ability of the polymer backbone to crystallize. This is further

explored in chapter 3 by examining the effect the length of the graft and the manner of its

connection to the backbone has on thermal behavior while keeping the graft end group constant.

Chapter 3 also showed that the saturation of the internal olefin influenced thermal behavior:

when the site of unstauration remains the polymers ability of to crystallize is greatly hindered or

suppressed completely. By considering these data we are able to constructed a model for the

manner in which the chains fold to allow the crystallization of the backbone and the exclusion of

the pendant branch. This chapter briefly describes the synthesis of deuterium labeled polymers

based on TEGOMe21 (structure 3-8b, presented in chapter 3). Solid state 2H NMR has been

utilized in the past to gain information on polymer molecular motions and dynamics.73-77 Since

TEGOMe21 presents both a well defined glass transition and melting endotherm it is an

excellent candidate for deuterium labeling and subsequent solid state 2H NMR motion studies on

the crystalline and amorphous regions of the polymer. Three labeled TEGOMe21analogues are

presented in this chapter. The backbone (midway between defects), the point of branch

connection, and the branch end group were chosen as labeling points since the previous chapters

have proven these locations are critical in the thermal behavior of these materials (Figure 5-1).

Only the synthesis of these polymers is discussed here, the solid state NMR experiments are

beyond the scope of this dissertation.









Experimental Section


Instrumentation

All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian

Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to

residual signals from CDC13 (1H: 6= 7.27 ppm and 13C: 6 = 77.23 ppm) with 0.03% v/v TMS as

an internal reference. Thin layer chromatography (TLC) was performed on EMD silica gel

coated (250 |tm thickness) glass plates. Developed TLC plates were stained with iodine

adsorbed on silica to produce a visible signature. Reaction conversions and relative purity of

crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR)

measurements were conducted with a Bruker Vector 22 Infrared Spectrophotometer using

polymer films cast from chloroform onto KBr plates. High resolution mass spectrometry

analyses were performed on a Bruker APEX II 4.7 T Fourier Transform Ion Cyclotron

Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization

(ESI). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA).

Molecular weights and molecular weight distributions (Mw 1 ) were determined by gel

permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid

chromatography system with an internal differential refractive index detector (DRI) and two

Waters Styragel HR-5E columns (10 micron particle diameter, 7.8 mm ID, 300 mm length) at 40

C. The mobile phase was HPLC grade tetrahydrofuran at a flow rate of 1.0 mL/minute.

Retention times were calibrated versus polystyrene standards (Polymer Laboratories; Amherst,

MA).

Differential scanning calorimetry (DSC) and temperature modulated differential scanning

calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid









nitrogen cooling accessory and calibrated using sapphire and high purity indium metal. All

samples were prepared in hermetically sealed aluminum pans (4-7 mg/sample) and were

referenced to an empty pan. Samples were run under a purge of helium gas. Scan rates of

10C/min and 3C/min were used for DSC and MDSC, respectively. Melting temperatures were

evaluated as the peak of the melting transition and glass transition temperatures as the mid-point

of a step change in heat capacity.

Materials.

Unless otherwise stated, all reagents were purchased from Aldrich and used without

further purification. Grubbs' 1st generation catalyst was a gift from Materia, Inc. Oligoethoxy-p-

tosylates59 and diene acid 5-449 were prepared according to the literature. 99TEGOMe (3-4b) and

99TEGOTs (4-2) were synthesized as described in chapters 3 and 4 of this dissertation,

respectively. 99CD20H (5-4) was prepared as described in the PhD dissertation of John

Sworen.76 TEGOMe21u (3-6b) was obtained from the polymerization of 99TEGOMe as

described in chapter 3 of this dissertation.

Synthesis of 99CD2TEGOMe (5-5).

Anhydrous DMF (40 mL) was cannula transferred into an oven dried, 3-neck round-

bottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents

of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and 2g (5.6

mmol) of 5-4 in 20 mL of anhydrous DMF was added via syringe. When gas evolution

(monitored by bubbler) ceased, 2.94g (8.1 mmol) of tetraethylene glycol monomethyletherp-

toluenesulfonate in 20 mL of anhydrous DMF was added via syringe. The reaction was stirred

for 17 hours at 0 OC and quenched by pouring into 300 mL of water. The resulting mixture was

extracted with diethyl ether and the combined organic washed with brine. Concentration

afforded a yellow oil which was further purified by column chromatography. 25% ethyl acetate









75% hexane eluent afforded .710g (23% yield) of colorless oil. 1H NMR (CDC13): 6 (ppm) 1.21-

1.52 (br, 33H), 2.01 (q, 4H), 3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 2H

NMR (CDC13): 6 (ppm) 3.30 13C NMR (CDC13): 6 (ppm) 26.92, 29.06, 29.27, 29.63, 29.73,

29.76, 30.20, 31.45, 33.94,38.22, 59.13, 70.50, 70.64, 70.71, 70.75, 72.07, 114.21, 139.29

ESI/HRMS: [M+H] calcd for H+C33H62D205, 543.4592; found 543.4933. Anal. (CH) calcd for

C33H6405: C, 73.01; H or D, 12.25. Found C, 72.94; H, 11.83.

Synthesis of 99TEGOCD3 (5-2)

Anhydrous DMF (40 mL) was cannula transferred into an oven dried, 3-neck round-

bottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents

of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and .270g (7.5

mmol) of deuterated methanol was added via syringe. When gas evolution (monitored by

bubbler) ceased, Ig (1.5 mmol) of 99TEGOTs (4-2) in 20 mL of anhydrous DMF was added via

syringe. The reaction was stirred for 17 hours at 0 OC and quenched by pouring into 300 mL of

water. The resulting mixture was extracted with diethyl ether and the combined organic washed

with brine. Concentration afforded a yellow oil which was further purified by column

chromatography. 25% ethyl acetate 75% hexane eluent afforded .300g (36% yield) of colorless

oil. 1H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.50-3.75 (br,

16H) 4.98 (m, 4H), 5.82 (m, 2H). 2HNMR (CDC13): 6 (ppm) 3.38 13C NMR (CDC13): 6 (ppm)

26.92, 29.06, 29.27, 29.63, 29.73, 29.76, 30.20, 31.45, 33.94,38.22, 70.50, 70.64, 70.71, 70.75,

72.07, 74.88, 114.21, 139.29 ESI/HRMS: [M+H]+ calcd for H+C33H6405, 544.5015; found

544.4998. Anal. (CH) calcd for C33H61D305: C, 72.88; H or D, 12.42. Found C, 72.66; H or D,

11.86









General Procedure for ADMET Polymerizations

Monomers were dried under vacuum at 80 OC for 48 hours prior to polymerization and

subsequently transferred to a 50 mL round-bottom flask equipped with a magnetic stir bar.

Grubbs 1st generation catalyst (300:1 monomer:catalyst ratio) was added and the flask was

stirred under vacuum at 45 C for 4 days. Polymerizations were quenched with ethyl vinyl ether

(5 drops in degassed toluene), precipitated into cold, acidic methanol to remove catalyst residue,

and isolated as an adhesive gum.

CD2TEGOMe21u.

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.35 (s, 3H), 3.50-3.75 (br,

16H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 27.03, 29.45, 29.76, 29.81, 29.90, 30.00,

30.32, 31.54, 32.83, 38.30, 59.22, 70.55, 70.71, 70.76, 70.80, 72.12, 130.05 (cis olefin), 130.52

(trans olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs.

Polystyrene standards): Mw = 63800 ; PDI (Mw/Mn) = 1.66

TEGOCD321u.

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.50-3.75 (br,

16H), 5.35 (m, 2H). 13C NMR (CDC13): 6 (ppm) 27.03, 29.45, 29.76, 29.81, 29.90, 30.00, 30.32,

31.54, 32.83, 38.30, 70.55, 70.71, 70.76, 70.80, 72.12, 74.96, 130.05 (cis olefin), 130.52 (trans

olefin). IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene

standards): 1 f,, = 88700 ; PDI ( f,1, .. ,) = 1.64

General Procedure for the TSH Hydrogenation of Unsaturated Polymers

Unsaturated polymers were dissolved in dry o-xylene. p-toluenesulfonyl hydrazide (TSH)

and tripropyl amine (TPA) were added with stirring (3 equivalents each). The resulting solution

was refluxed for 3-4 hours while monitoring nitrogen evolution with a bubbler. When gas









evolution ceased, the solution was cooled to room temperature, an additional 3 equivalents of

TSH and TPA were added, and the solution was refluxed for another 3 hours. The solutions were

then concentrated to one-half of the original volume and precipitated into cold, acidic methanol.

The polymers were isolated as elastic, adhesive gums.

CD2TEGOMe21 (5-7).

1HNMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H), 3.35 (s, 3H), 3.50-3.75 (br, 16H). 13C

NMR (CDC13): 6 (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 59.25, 70.61, 70.76, 70.83, 70.86,

72.18, IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene

standards): M, = 77700 ; PDI (M/.\ )= 1.70

TEGOCD321 (5-3).

H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.50-3.75 (br, 16H). 13C

NMR (CDC13): 6 (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 70.61, 70.76, 70.83, 70.86, 72.18,

75.03. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene

standards): M, = 107500 ; PDI (I1,, -1 ) = 1.66

Parr Bomb "Deuteration" of TEGOMe21d (5-1).

Unsaturated, trityl protected polymer TEGOMe21u was dissolved in toluene and added to

a glass lined Parr bomb. Wilkinson's catalyst was added and the bomb charged with 700 psi of

D2. The reaction was stirred for 3 days at room temperature. The resulting polymers were

purified by precipitation into acidic methanol to remove catalyst residue and isolated as an

adhesive gum. 1H NMR (CDC13): 6 (ppm) 1.21-1.52 (br, 39H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-

3.75 (br, 16H). 13C NMR (CDC13): 6 (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 59.25, 70.61,

70.76, 70.83, 70.86, 72.18, 75.03. IR (v cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC

(THF vs. Polystyrene standards): M, = 81700 ; PDI (M.\ 1 )= 1.70









Results and Discussion


Synthesis and Structural Analysis

Figure 5-2 illustrates the synthesis of the deuterium labeled TEGOMe21 analogues. To

label the backbone TEGOMe21u (3-6b, prepared as described in chapter 3) was simply saturated

with deuterium gas using the parr bomb hydrogenation procedure found in chapter 2. Labeling

the branch's methyl end group and the branch connection point were slightly more complicated.

To label the branch end group 99TEGOTs (4-2, prepared as described in chapter 4) was reacted

with deuterated sodium methoxide. To label the branch connection the appropriately labeled

diene alcohol 99CD20H (5-5) was prepared by the LAD reduction of the diene acid 5-4. This

alcohol was then used in a Williamson etherification to yield 99CD2TEGOMe, the reaction

conditions identical to the synthesis of the corresponding unlabeled monomer described in

chapter 3.

The structures of the deuterium labeled monomers were confirmed by 1H, 13C, and 2H

NMR as well as high resolution mass spectrometry and elemental analysis. Figure 5-3 shows the

1H NMR spectra of the deuterium labeled monomers with the unlabeled 99TEGOMe for

comparison. In the spectrum for 99CD2TEGOMe the doublet at 6=3.29 ppm corresponding to

the methylene unit directly off the backbone disappears confirming deuterium labeling at this

location. In the spectrum of 99TEGOCD3 the singlet at 6=3.35 ppm corresponding to the branch

methyl end group is absent, confirming the presence of deuterons at this location.

Similarly, differences in the 13C NMR spectra (Figure 5-4) between the labeled and unlabeled

can be seen. Labeling at the methylene unit and methyl end group results in the splitting of the

corresponding carbon signal, slightly visible in the spectrum for 99CD2TEGOMe (6=75 ppm)









and not visible in the spectrum for 99TEGOCD3 (6=59 ppm). In both cases the disappearance of

the obvious singlets confirms deuterium labeling has occurred on these carbons

As discussed in the chapter 3 (Figure 3-6), polymerization is confirmed by the

disappearance of terminal olefin signals in both the 1H and 13C NMR spectra. Subsequent

saturation is confirmed by the disappearance of the internal olefin signal.

Thermal Analysis

Since the ultimate goal of this synthesis is to study the dynamics above and below the glass

transition and melting temperatures it is essential to confirm that labeling in this fashion will not

affect these polymers' thermal response. Figure 5-5 shows the DSC overlay for all three labeled

polymers. It is clear looking at the thermogram that the thermal behavior is identical in all cases,

showing that labeling in this fashion does not alter the thermal behavior of the polymer. Given

the consistency in the thermograms it is clear these materials are appropriate for future use in

solid state 2H NMR motion studies.

Conclusions

The polymer TEGOMe21 was deuterium labeled in three locations that have been proven

critical throughout this dissertation in the crystallization and melting behavior of this class of

materials. The deuterium labeling of these ADMET amphiphiles is straight forward and requires

only small alterations in synthetic method. Labeling in the fashion does not affect the thermal

behavior of the final polymer. These materials could be useful in solid state 2H NMR motion

studies. Such studies could offer further insight into the way these specific locations on the

repeat unit of ADMET polymers affect the crystallization and melting behavior.











0---O---O--O---Oe

MeO0,--O~0--O

0~0/c0~fi


Backbone
labeled


Connection
labeled


Branch end
group labeled


Figure 5-1: Locations chosen for deuterium labeling in TEGOMe21

Deuterium Labeled Backbone


99T e
99TEGOMe (3-4b)


0-0

9 9
TEGOMe21u (3-6b)


D
Sd 4
D 9 9
TEGOMe21 d (5-1)


Deuterium Labeled Methyl Group

Of -OTs O OCD3

99 9 -
99TEGOTs (4-2) 99TEGOCD3 (5-2)


1. i
2. iv


---OOCD3
TE O D 2 n 4
9 9
TEGOCD321 (5-3)


Deuterium Labeled Methylene Unit


O OH



5-4


OH
D0

Sn fl
99CD20H (5-5)


Vi D0 2. iv n4-
^4 n 4
'n f 9 9
99CD2TEGOMe (5-6) CD2TEGOMe21 (5-7)


Figure 5-2: Synthesis of deuterium labeled TEGOMe21 analogues; i: Grubbs 1st generation, 45
OC, vacuum; ii: Wilkinson's catalyst; 700 psi D2, toluene; iii: NaH, CD30D, DMF; iv:
TSH, TPA, xylenes, 140 oC; v: LAD, THF; vi: NaH, TsO(CH2CH20)4CH3, DMF










unlabeled monomer 99TEGOMe


6 A H
H H
G
C
D


A B EI F


deuterated
methylene unit
99 CD2TEGOMe
Peak "E"

appear

Adoes not
deuterated
methyl group
99TEGOCD3 Peak"D"
does not
E appear


I I I . I l. I l.. I I '
6.0 5.0 4.0 3.0 2.0 1.0
ppm

Figure 5-3: 1H NMR of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe
shown for comparison










unlabeled monomer
99TEGOMe


A o B
4

9 9


A B


deuterium labeled
methylene unit
99CD2TEGOMe
__2


deuterium labeled
methyl group
99TEGOCcD


ppm 80 70 60 50


Figure 5-4: 13C spectra of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe
shown for comparison


ccu~rrcr~~*vcryc~C~3*rcrmc-r~h*















i_ Y,_-2 ..........





1 -1


-2

-100o -50 0 50
Temperature ("C)


Figure 5-5: DSC overlay of the deuterium labeled TEGOMe21 analogues.









APPENDIX
IMPRESSIONS ON LIFE IN KYOTO

Hajimemashite

As long as I live I will never forget the shouts of irrashaimassen dozo when entering

restaurants or shops, or the chants of arigato gozimasu received when leaving. Although I spent

only one month in Japan it has left an indelible impression. The entire society is set up for

efficiency and convenience. There is intense emphasis on being polite, as well as a strong feeling

that the collective is much more important than the individual. This is not to say that

individuality is not openly expressed and embraced. It is simply slightly more subtle than in

western cultures. There are wisdoms and courtesies to Japanese culture that escape our own.

People with colds, for example, wear gauze masks to protect others from infection. The emphasis

on politeness can be aggravating to an unfamiliar outsider, and could even be misconstrued as

open rudeness. For example, no one will tell you "no." They instead say: musukashi desu ne

(literally "it's difficult"). Chotto musukashi desu (it's a little difficult) appears to mean down

right impossible. Imagine asking if the train you are on goes to your destination and being told

that "it's a bit difficult," only to find out after continuing to ride that is does not take you

anywhere close to where you want to be. Once you begin to recognize the social rules and adopt

them in your own behavior the atmosphere is warm and inviting.

Japan is not at all free of Western influence, however. Kyoto, Osaka and Nagoya have the

same designer fashion boutiques as Fifth Avenue in Manhattan. The music shops are lined with

rare and vintage American guitars. Camera shops contain high end professional equipment from

all over the globe. Appearance, it seems, is very important. At the same time, stealing in Japan is

unheard of. In Kyoto I lost a cellular phone on a bus and it was returned to me within days. The

lack of thievery coupled with this emphasis on materialism perhaps reveals the most striking trait









of Japanese culture: everything from possessions to social status must be earned through hard

work, honor, and integrity.

Amid the vast differences are innumerable and comforting similarities. It took no time at

all for me to feel at home despite my sophomoric understanding of the language. In the following

report I will briefly describe the cultural experience I had during my visit. This exchange has

changed my outlook entirely. I can not wait to return for an extended visit, and I have

recommended the trip to everyone I've talked to since my return. To spend time in another

culture is essential to understand how small the world we share really is, how alike we all are,

and how much we still have to learn from each other. For a graduate student this is of

monumental importance, as many of us become the educators of future generations. We can not

teach understanding and tolerance for all people until we are forced to tolerate and understand, as

well as be tolerated and understood. My experience in Kyoto has promoted precisely this.

City life in Kyoto

I was immediately impressed by the cleanliness of the city, the efficiency of the public

transportation, and the ease at which this city of about 1.5 million operates. The subway system

consists of only 2 lines, which is in sharp contrast to the complicated network of train lines in

Nagoya or Osaka. Busses are by far the easiest means of transport. They are always on time,

reasonably priced (roughly 2 American dollars for most rides), and on city busses a number of

stops are announced in English. Several private bus lines link to private and public train lines,

making travel to surrounding areas very convenient.

Restaurants in Kyoto operate with the same efficiency as the public transportation. You are

welcomed with tea, your order taken, and your check delivered with the food. There is no

pressure to hurry, however the minute you stand up your table is bussed and prepared for the

next customer. Tipping is not customary. The cost of food varies widely. Family sit down









restaurants (comparable to Applebee's or Ruby Tuesday's in the US) are about 30% more

expensive, the cost per meal around 12-15 USD. Higher quality restaurants (comparable to our

downtown restaurants like Liquid Ginger) are much more expensive, typically 30-50 USD for a

meal. At some of the more famous sushi restaurants patrons can expect to pay upwards of $500

per person for the experience! Most restaurants of course feature Japanese food, however

Chinese, French, and Italian cuisine are all very popular throughout Japan.

Japanese fast food is similar in cost to US fast food, depending on the meal item and

portion. The food is much lower in fat content compared to US fast food. Food at grocery stores

is again comparable to US prices, with the exception of beef, which is extremely expensive in

Japan. Some western items are widely available such as breakfast cereal and potato chips;

however it is difficult to find all of the ingredients to cook traditional American meals.

Entertainment is Kyoto is slightly lower key than other Japanese cities. There are a few

pubs, bars, and night clubs. I didn't frequent these, preferring instead to explore the myriad

temples, shrines, and shopping arcades for a true look into a foreign culture with a fascinating

history. Perhaps the most interesting feature was the vast subterranean malls in Kyoto and

Nagoya. In such a small country space is a premium, and the Japanese are experts and making

the most efficient use of this resource.

Graduate School in Kyoto

The educational system in Japan is very different from our own system. Research groups

are run by a team of three faculty members: one full professor, one associate professor, and one

assistant professor. There is always more faculty on staff than at American research universities;

Osaka University's department of Materials Engineering has 60 full professors alone (180

professors if assistant and associate professors are included!)









Students remain at the same school throughout undergraduate, masters, and PhD studies.

They are required to finish masters studies before working towards a PhD; most students elect to

take an industrial job rather than continuing for a PhD. Regardless of the difference in structure

the time to a degree is about the same: Japanese graduate students spend 2 years in the masters

course and 3 years in the PhD course. All of this time is spent on research, there is no teaching

requirement.

Life as a graduate student in Japan is not at all unlike life as an American graduate student

in the sciences. Most students work 10 to 12 hours days, most work at least one day on the

weekend. Some students arrive early, most however begin work around 10 am. This varies from

group to group, just like in the USA. The most striking difference to our university is the time for

weekly group meeting: in Japan research groups meet every other Saturday to discuss research.

The purpose is 2 fold, it allows every researcher ample time to discuss recent work and get

advice, as well as forcing less diligent students to work at least 2 Saturdays a month! In addition,

each researcher is expected to give a literature presentation every semester. There is great

emphasis on being productive, and a total of 6 publications, split between undergraduate,

masters, and PhD courses are expected before a PhD degree will be awarded. The length and

style of PhD dissertations is very similar to those in the USA, and most are written in English.

College Sports at Kyoto University

I was fortunate enough to join Kyodai Judo Club for one of their practices and get a

glimpse into role of extra curricular activities and athletics at Japanese colleges. There is really

no equivalent at Japanese universities for NCAA college athletics. All sports are operated as

clubs. The members, however, take them just as seriously as our college athletes (perhaps more

so!) The Kyodai Judo team practices 6 days a week for at least 3 hours per session. Every other

week there are 2 practice session per day Monday through Friday. This is true not only for









Japanese sports such as judo, kendo, and karate, but also western sports like boxing, fencing,

volleyball, basket ball, etc. Music and art clubs operate with the same intensity. I was curious

how this affected course work; apparently undergraduate studies are very different in Japan. The

most rigorous part is the entrance exam. The course work is less intense than in the USA, the

idea being that Undergraduate time is supposed to be enjoyed before the responsibilities of

professional life set in.

Benefit to the University of Florida

The benefits of this exchange program to both the students involved as well as the

University of Florida itself far outweigh the costs involved. Kyoto University is one of the top

ranked schools in Asia (second only to the University of Tokyo), as well as being ranked in the

top 25 schools in the world.

For students, this program allows a glimpse at a different culture with a fascinating history.

For students in science particularly this is an eye opening experience, as the lingua franca for the

sciences is English. At the poster sessions I attended a number of the presentations reflected this.

Although a majority the lectures were in Japanese, most of the power point slides were in

English, so it wasn't difficult to follow their stories. I even attended a few symposia were the

language switched from Japanese to English between speakers (questions and discussions

included)! Perhaps most surprising was the fact that these English lectures were usually given by

Chinese or Korean speakers. It is especially important for American students to witness this.

How many of us could enter into scientific discussions in multiple languages?

The University of Florida also benefits by strengthening its bond with a globally

recognized institution. Kyoto University has been involved in exchange programs with Stanford,

Brown, The University of Pennsylvania, the University of Michigan, Oxford, and Cambridge to









name a few. The University of Florida certainly belongs among such company, and I hope that

we will continue to build this connection with colleagues at Kyoto University.

Arigato Gozaimashita

I would like to extend my gratitude to Professors Masuda, Sanda, and Shiotsuki for their

hospitality, as well and the Deans office, the College of Liberal Arts and Sciences, and my

advisor Ken Wagener for making this dream a reality. I am a changed person after my

experience in Japan and I hope I can incorporate the lessons of patience, tolerance, respect, and

curtsey I learned during my visit in all of my future endeavors.









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BIOGRAPHICAL SKETCH

Erik Benjamin Berda was born in Scranton, PA on September 12th, 1980. Shortly after,

parents Pat and Marybeth Berda relocated to the Northwest Suburbs of Philadelphia, where Erik

spent the remainder of his youth. He discovered chemistry during sophomore year of high school

and became immediately enamored. Erik graduated from Norristown Area High School in June,

1999. He began studies towards a Bachelor of Science Degree in chemistry at Penn State

University (PSU), University Park Campus, in August 1999.

During his second year at PSU he joined the research group of Prof. Harry R. Allcock,

studying phosphazene based polymers for advanced lithium battery applications. Erik also

developed a deep passion for teaching at PSU giving guitar lessons. This translated fluidly into

science while teaching a section of organic lab in the spring of his senior year.

After graduating from PSU in December 2003 Erik moved to the University of Florida in

Gainesville to pursue a PhD degree in Organic Chemistry under the advisement of Prof Kenneth

B. Wagener. During his tour of duty in Gainesville, the state of Florida endured record numbers

of hurricanes, wild fires, and fatal alligator attacks. Despite this, the University's own Gators

managed to capture a record number of NCAA national titles.

In September 2007 Erik spent a month at Kyoto University in Kyoto, Japan. He

successfully completed the requirements for the PhD degree in March of 2008. After graduation

he moved to Europe with longtime girlfriend Dana Gioia to begin postdoctoral studies with Prof.

Bert W. Meijer at the Technical University of Eindhoven in Eindhoven, The Netherlands.





PAGE 1

1 ADMET AMPHIPHILES By ERIK BENJAMIN BERDA A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2008

PAGE 2

2 2008 Erik Benjamin Berda

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3 To Dana, the love of my life, for her sacrif ices, love, support, and understanding and to Bethy, Patty, and Mikey for lots of help along the way.

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4 ACKNOWLEDGMENTS There are many a great folken whom helped m e along the way both here in Gainesville and back in Pennsylvania, say thankya. Ill start in Gainesville and work my way backwards in a pseudo-chronological fashion. First Id like to acknowledge the Department of Chemistry, in particular Ben Smith, Ken Wagener, John Reynolds, and Randy Duran. They saw potential when no other institution would give me a chance. I am eternall y grateful for your confidence. I would again like to thank Ken Wagener fo r his patience; I am a stubborn and often intolerable student. He forgave my frequent tr espasses, and I learned a great deal about mentoring from him. I would also like to ac knowledge John Reynolds. It has been a pleasure working under two capable advisors and I truly appreciate the opportunities I was presented with working in the Butler Labs (a.k.a. the artist form erly known as Polymer Floor). Also I would like to thank George Butler, rest pe acefully, and his wife Josephine for their contributions to our program. I would like to thank the rest of my committee: Bill Dolbier, Mike Scott, and Tony Brennan for there time, effort, and advice. I would especially like to thank Bill Dolbier; I really began to understand organic chemistry during hi s 5224 class. I would also like to acknowledge Tammy Davidson and Eric Scriven, it has been a pleasure serving as a TA for both of you. The road through Gainesville would not have been to lerable if it were no t for great friends. Thank you to Travis Baughman for splitting the rent, talking Wagener group, and rocking the endless blues in E. Thank you to Jeremiah Tipton for the best rendition of Spoonman ever. Thanks to Ben Reeves for low key low tones, the Wednesday jams are severely missed. Thanks to his lovely wife Jenny for beating me Texas Holdem repeatedly. Thank you to Josh McClellan for philosophical discussions while nearly fre ezing to death in the November North Georgia woods. Thanks to Piotr and Nela Matloka for go od lunches, good parties, and being great hosts

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5 in Belgium. Id like to thank James Leonard fo r showing me that you can actually load 2 20 ga. Rounds into a 12 ga. Shotgun, pull th e trigger, and live to laugh about it. Thanks to Giovanni Rojas for tons of laughs in Pasadena. Id like to thank Flo Courchay for consistent kind remarks. Thank you to Kate Opper for turtle sitting, dog lending, and spilling appletinis on my carpet. Thank you to Sam Popwell for good laughs during the summer 07 teaching labs, What Would Bear Do? Thank you to YuYing Wei for an anal ytical chemists perspective on synthetic chemistry, Ill stop cleaning spatul as with my gloves now. Thanks to Paula Delgado for showing me the inherent flaws in the DSC sample pre ss design. I would like to thank Zach Kean for good times at T&Ts. Thank you to the newest members of the Wagener Mafia: Bora and Brian, it was nice to get to know you over the past several mo nths. Id like to thank Bob Brookins and Tim Steckler for good laughs at the Seminole Hard Rock Casino. Thanks to The German for sharing a few small pitchers between enormous chroma tography sessions. Thank you to Pierre, Jianguo, June, and Prasad for making 322/324 a great place to make polymers. Thanks to Merve Ertas for constructive criticism and entertaining use of the English language. Thank you to Sophie Bernard for being just sarcastic enough. Id like to thank JJ Cowart for help with some polymerizations. Also, thank you to Eva and Mike hanging out and listening to the Beatles. Thanks to Violeta Petkovska for great conversation and even headed advice. I cant forget to thank Rachel Lande for being a great student, even when I was not such a great mentor. The gentle way kept me sane during my tour of duty in Gainesville. I would like to thank Matt and Lauren, Davis and Virg inia, Ed and Carissa, Thomas and Cathy, Larry and Ana, Weber, Chris, Chan, and Natty for being great teac hers and great friends. Thank you to the entire UF Judo club past and present, it has been excep tional to train with such superb judoka.

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6 Thank you to all of my colleagues from the Po lymer Floor, Organic Division, and the rest of the department that I may have inadverten tly neglected to menti on. I could fill an entire dissertation thanking such a wonde rful group of individuals. Work would come to a grinding halt in this place if it werent for the efforts of some amazing administrative assistants. In the polymer office Sara Klossner and Gena Borrero, we know who really runs the show, thank you for your hard work. Also, thank you to Lori Clark in the Graduate Office and Maribel Lisk in the Chai rmans office for all of your help as well. Special thanks go to Toshio Masuda, Fu mio Sanda, Masashi Shiotsuki, Kimiko Tada, Kayo, Suzuki, Matty, the rest of the Masuda La b, and Kazushi Mashima for being great hosts and great friends during my trip to Kyoto. I cant wa it to return. From Pennsylvania there are a number of people to whom I am forever in debt. Of course, my parents Pat and Marybeth, one couldnt ask for better teachers and friends. Also, thanks are in order for my brother and best friend Mike Berd a. I couldnt leave out Clarkie, thanks for all your love and support, nor the GrandBerdas, thanks for the prayers. Of course this section wouldnt be complete without thanking the rest of the family, Jay DeFrangesco, Nick Pisano, and Dan Watson. My mind wanders to Norristow n circa 1997 often, thank you for being great friends. In addition, I would like to thank L ynn Hinely, Joseph DeFrancesco, and Ron Petruso for being great teachers and really shap ing what would be my career choice. From Penn State I would like to acknowledge Harry Allcock, Bob Morford, and Eric Powell for my introduction to polymer research. Also, I would like to thank Bob Minard for giving me a shot at teaching organic lab, also Dan Sykes for being a patient educator. I would like to thank Steven Babcock for the only F I had to fight to recieve.

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7 From Watts Hall to 333 thank you to Tom Riccairdi, Brian Boyle, Mark Lupinacci, Bryan Koval, Aaron Pressman, Mike Carroll, Patty Sal imone, Jessica Summers, and Hillary Ryan. My memories of this time are fond and I think of you all often. I wouldnt have made it through PSU without you. The thirty pounds I gained eating DP dough was worth it. I would also like to thank Arie Hawkins and the crew at the college fo rmerly known as WMC. Westminster Maryland was an experience in and of itself. Thank you to the I&C group at Limerick Genera ting Station, the opportunity to work here was amazing and I will never fo rget it. I totally understand Dilbert and Office Space after this experience. From 1011 to UC building C Id like to thank Geoff Faden, Jason Drews, E, Rob Lanning, Steve Kulada, Tracey Johnson, Josie, Luis Tito, Santana, Punishment, Ace, Tre Diggs, Laura Merrick, and of course Mecca. These times were unforgetable. The extra semester it cost was worth it. There are some people from Marios that can not go unmentioned. Thank you to Melody Phillips, Michelle, Scott, Ralph, Linda, Gail, an d Tracey Faye; it was awesome to meet and work with you. Of course I can not forget Tom at the end of the bar for good c onversation over several glasses of vino. Marios is special to me for another reason; this is where I met Dana. I knew from the moment I met you. Thank you for your constant l ove and encouragement; you mean the world to me. Of course I cant leave out my family on Elm Street: Denny, Judy, and Erin. Thanks for sharing your lives; I am actually growing to enjoy playing board games.

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8 Science is the pursuit of the truth; howeve r the truth itself is unapproachable by any one path To me, this is the meaning of the degree Doct or of Philosophy; the art we choose is simply the way we walk My deepest gratitude for walking with me, I could not have done it alone.

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9 TABLE OF CONTENTS page ACKNOWLEDGMENTS...............................................................................................................4 LIST OF TABLES................................................................................................................. ........14 LIST OF FIGURES.......................................................................................................................15 ABSTRACT...................................................................................................................................18 CHAP TER 1 INTRODUCTION..................................................................................................................20 The Evolution of ADMET...................................................................................................... 20 Linear ADMET Polyethylene.................................................................................................23 Model Polyolefins with Preci sely Placed Halogen Atom s..................................................... 24 Precise Fluorine Placement............................................................................................. 24 Precise Chlorine Placement............................................................................................. 25 Precise Bromine Placement............................................................................................. 25 Model Polyolefins with Preci sely Placed Alkyl Branches ..................................................... 26 Precise Methyl Placement: ADMET Ethyl ene Propylene (EP ) Copolymers.................. 26 ADMET Polyolefins with Larger Alkyl Defects.............................................................29 Precise Geminal Di m ethyl Placement............................................................................. 29 Precise Ethyl Branch Placement...................................................................................... 29 Precise Hexyl Branch Placement..................................................................................... 30 Precise Ether Placement.................................................................................................. 32 Toward Advanced Applications.............................................................................................32 Precise Carboxylic Acid Placement................................................................................ 32 Precise Ionomers............................................................................................................. 33 Purpose of Study.....................................................................................................................34 2 ADMET AMPHIPHILES: POLYETHYLEN E W ITH PRECISELY PLACED HYDROPHILIC DEFECTS...................................................................................................49 Introduction................................................................................................................... ..........49 Experimental Section........................................................................................................... ...51 Instrumentation................................................................................................................ 51 Materials..........................................................................................................................52 General Procedure for the Synthesis of Trityl Protect ed Tetra(ethylene glycol) Monom ers....................................................................................................................52 2-(4-pentenyl)-6-heptenyl-1-tetra(ethyl ene glycol) m onotrityl ether (2-2a)............ 53 2-(7-octenyl)-9-decenyl-1-tetra(ethylen e glycol) monotrityl ether (2-2b). .............. 53 2-(10-undecenyl)-12-tridecenyl-1-tetra(eth ylene glycol) m ono trityl ether (22c).........................................................................................................................53 General Procedure for ADMET Polymerizations........................................................... 54

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10 Polymerization of 2-(4-pentenyl)-6-h eptenyl-1-tetra(ethylene glycol) monotrityl ether (TEGOTr9u, 2-3a). .................................................................... 54 Polymerization of 2-(7-octenyl)-9-decenyl-1-t etra(ethylene glycol) m onotrityl ether (TEGOTr15u, 2-3b)..................................................................................... 54 Polymerization of 2-(10-undecenyl)-12trideceny l-1-tetra(ethylene glycol) monotrityl ether (TEGOTr21u, 2-3c)...................................................................55 General Procedure for Parr Bomb Hydrogenation of Unsaturated Polymers................. 55 TEGOTr9 (2-4a).......................................................................................................55 TEGOTr15 (2-4b).................................................................................................... 56 TEGOTr21 (2-4c)..................................................................................................... 56 General Procedure for the Remova l of the Trityl Protecting G roup............................... 56 TEGOH9 (2-5a)........................................................................................................56 TEGOH15 (2-5b).....................................................................................................57 TEGOH21 (2-5c)......................................................................................................57 Results and Discussion......................................................................................................... ..57 Synthesis and Structural Analysis...................................................................................57 Thermal Analysis.............................................................................................................59 Conclusions.....................................................................................................................62 3 PROBING THE EFFECTS OF PENDANT B RANCH LENGTH, DISTRIBUTION, AND CONNECTIVITY IN ADMET AMPHIPHILES......................................................... 70 Introduction................................................................................................................... ..........70 Experimental Section........................................................................................................... ...72 Instrumentation................................................................................................................ 72 Materials..........................................................................................................................74 General Procedure for the Synthesis of Methoxy Term inated PEG Grafted Diene Monomers (3-3a-d, 3-4a-d).......................................................................................... 74 9-(tetra (ethylene glycol) monome thyl ether)-1,1 6-heptad ecadiene (6,6TEGOMe2, 3-3a)............................................................................................ 74 12-(tetra (ethylene glycol) monom ethyl ether)-1,22-tricosadiene (9,9TEGOMe2, 3-3b)........................................................................................... 75 9-(tri (ethylene glycol) monome thyl ether)-1,16-heptadecadiene (6,6TrEGOMe2, 3-3c). ......................................................................................... 75 12-(tri (ethylene glycol) monomethyl ether)-1,22-tricosadiene (9,9TrEGOMe2 3-3d). .....................................................................................................................75 2-(7-octenyl)-9-decenyl-1-tetra(ethylene glycol) monomethyl ether (6,6TEGOMe, 3-4a).............................................................................................. 76 2-(10-undecenyl)-12-tridecenyl-1-tetra (ethylene glycol) m onomethyl ether (9,9TEGOMe, 3-4b)............................................................................................. 76 2-(7-octenyl)-9-decenyl-1-tri(et hylene glycol) m onomethyl ether (6,6TrEGOMe, 3-4c)............................................................................................ 76 2-(10-undecenyl)-12-tridecenyl-1-tri (e thylene glycol) m onomethyl ether (9,9TrEGOMe, 3-4d)............................................................................................77 General Procedure for ADMET Polymerizations........................................................... 77 Polymerization of 9-(tetra (ethyl ene glycol) m onomethyl ether)-1,16heptadecadiene (TEGOMe15u2, 3-5a).................................................................77

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11 Polymerization of 12-(tetra (ethylene glycol) m onomethyl ether)-1,22tricosadiene (TEGOMe21u2, 3-5b)...................................................................... 78 Polymerization of 9-(tri (ethylen e glycol) m onomethyl ether)-1,16heptadecadiene (TrEGOMe15u2, 3-5c)................................................................ 78 Polymerization of 12-(tri (ethylene glycol) monomethyl ether)-1,22tricosadiene (TrEGOMe21u2, 3-5d). .................................................................... 78 Polymerization of 2-(7-octenyl)-9-d e cenyl-1-tetra(ethylene glycol) monomethyl ether (TEGOMe15u, 3-6a).............................................................. 79 Polymerization of 2-(10-undecenyl)-12-tr ideceny l-1-tetra (ethylene glycol) monomethyl ether (TEGOMe21u, 3-6b)..............................................................79 Polymerization of 2-(7-octenyl)-9-dece nyl-1-tri(ethylene glycol) m onomethyl ether (TrEGOMe15u, 3-6c)..................................................................................79 Polymerization of 2-(10-undecenyl)-12trideceny l-1-tri (ethylene glycol) monomethyl ether (TrEGOMe21u, 3-6d)............................................................. 79 General Procedure for the Hydroge nation of Unsaturated Polym ers.............................. 80 TEGOMe152 (3-5a)................................................................................................. 80 TEGOMe212 (3-5b)................................................................................................. 80 TrEGOMe152 (3-7c)................................................................................................81 TrEGOMe212 (3-7d)................................................................................................81 TEGOMe15 (3-8a)................................................................................................... 81 TEGOMe21 (3-8b)................................................................................................... 81 TrEGOMe15 (3-8c)..................................................................................................81 TrEGOMe21 (3-8d)..................................................................................................82 Results and Discussion......................................................................................................... ..82 Synthesis and Structural Analysis...................................................................................82 Thermal Analysis.............................................................................................................85 Conclusions.....................................................................................................................88 4 INDUCING PENDANT BRANCH SELF AS SE MBLY IN ADMET AMPHIPHILES..... 100 Introduction................................................................................................................... ........100 Experimental Section........................................................................................................... .102 Instrumentation.............................................................................................................. 102 Materials........................................................................................................................103 Synthesis of 2-(10-undecenyl)-12-tr idecenyl-1-tetra(ethy lene glycol)p-tosylate (42)................................................................................................................................103 General Procedure for Preparation of Monomers......................................................... 104 2-(10-undecenyl)-12-tridecenyl-1-tetra (ethylene glycol) m ethenyl pyrene (9,9TEGOPy, 4-3a)............................................................................................. 104 2-(10-undecenyl)-12-tridecenyl-1-tet ra (ethylene glycol) m ono n-hexyl ether (9,9TEGOHex, 4-3b)..........................................................................................105 2-(10-undecenyl)-12-tridecenyl-1-tet ra (ethylene glycol) m ono n-tetradecyl ether (99TEGOC14, 4-3c)....................................................................................105 General Procedure for ADMET Polymerizations......................................................... 106 Polymerization of 2-(10-undecenyl)-12-tr ideceny l-1-tetra (ethylene glycol) methenyl pyrene (TEGOPy21u, 4-4a)................................................................ 106

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12 Polymerization of 2-(10-undecenyl)-12-tr ideceny l-1-tetra (ethylene glycol) mono n-hexyl ether (TEGOHex21u, 4-4b).........................................................106 Polymerization of 2-(10-undecenyl)-12-tr ideceny l-1-tetra (ethylene glycol) mono n-tetradecyl ether (TEGOC1421u, 4-4c)................................................... 107 General Procedure for the Hydroge nation of Unsaturated Polym ers............................ 107 TEGOPy21, (4-5a).................................................................................................107 TEGOHex21 (4-5b)................................................................................................108 TEGOC1421 (4-5c)................................................................................................. 108 Results and Discussion......................................................................................................... 108 Synthesis and Structural Analysis.................................................................................108 Thermal An alysis ........................................................................................................... 111 Conclusions...................................................................................................................113 5 SYNTHESIS OF DEUTERIUM LA BELED ADMET AMPHIPHILES ............................ 126 Introduction................................................................................................................... ........126 Experimental Section........................................................................................................... .127 Instrumentation.............................................................................................................. 127 Materials........................................................................................................................128 Synthesis of 99CD2TEGOMe (5-5)............................................................................... 128 Synthesis of 99TEGOCD3 (5-2)....................................................................................129 General Procedure for ADMET Polymerizations......................................................... 130 CD2TEGOMe21u................................................................................................... 130 TEGOCD321u........................................................................................................130 General Procedure for the TSH Hydrogenation of Unsaturated Polymers................... 130 CD2TEGOMe21 (5-7)............................................................................................ 131 TEGOCD321 (5-3).................................................................................................131 Parr Bomb Deuteration of TEGOMe21d (5-1)..........................................................131 Results and Discussion......................................................................................................... 132 Synthesis and Structural Analysis.................................................................................132 Thermal An alysis ........................................................................................................... 133 Conclusions...........................................................................................................................133 IMPRESSIONS ON LIFE IN KYOTO....................................................................................... 138 Hajimemas hite .................................................................................................................. ....138 City life in Kyoto............................................................................................................. .....139 Graduate School in Kyoto....................................................................................................140 College Sports at Kyoto University...................................................................................... 141 Benefit to the University of Florida...................................................................................... 142 Arigato Gozaimashita........................................................................................................... 143 LIST OF REFERENCES.............................................................................................................144 BIOGRAPHICAL SKETCH.......................................................................................................149

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13

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14 LIST OF TABLES Table page 1-1 Effect of molecular weight on therm al behavior in linear ADMET polyethylene............ 47 1-2 Precise halogen family DSC data......................................................................................47 1-3 Precise methyl family DSC data........................................................................................47 1-4 Precise geminal -dim ethyl family DSC data....................................................................... 47 1-5 Precise ethyl family DSC data........................................................................................... 48 1-6 Precise hexyl family DSC data.......................................................................................... 48 1-7 Precise ether family DSC data........................................................................................... 48 1-8 Precise carboxylic acid family DSC data........................................................................... 48 2-1 Molecular weight data for polymers described in chapter 2..............................................69 2-2 DSC data for polymers described in chapter 2..................................................................69 3-1 Molecular weight data for polymers described in chapter 3.............................................. 99 3-2 DSC data for polymers described in chapter 3.................................................................. 99 4-1 Molecular weight data for polymers described in chapter 4............................................ 125 4-2 DSC data for polymers described in chapter 4................................................................ 125

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15 LIST OF FIGURES Figure page 1-1 Olefin metathesis reactions................................................................................................ 37 1-2 The ADMET polycondensation reaction........................................................................... 37 1-3 Well defined metathesis catalysts...................................................................................... 38 1-4 The ADMET mechanism................................................................................................... 38 1-5 ADMET polymerization/hydrogenation stra tegy for precision polyolefin models ...........39 1-6 Nomenclature used in this introduction for ADM ET polymers........................................39 1-7 Precise halogen family.......................................................................................................39 1-8 Precise methyl family...................................................................................................... ..40 1-9 Synthesis of ADMET EP models...................................................................................... 40 1-10 DSC comparison of random and precise EP polym ers with similar branch content......... 41 1-11 Precise geminal -dim ethyl family....................................................................................... 41 1-12 Precise ethyl family...................................................................................................... ......42 1-13 Precise hexyl family...................................................................................................... .....42 1-14 DSC comparison of Et21 and Hex21.................................................................................43 1-15 Model for the crystallization of ADM ET polyolefins with larger defects......................... 44 1-16 Precise ether family...................................................................................................... ......44 1-17 DSC comparison of OMe21 and Et21............................................................................... 45 1-18 Precise carboxylic acid family........................................................................................... 45 1-19 Target morphology......................................................................................................... ....46 2-1 Polymer Synthesis. ......................................................................................................... ....63 2-2 The 1H NMR spectrum of 6,6TEGOTr..............................................................................63 2-3 Progression of monomer (6,6TEGOTr) to polym er (TEGOH15) monitored by 1H NMR..................................................................................................................................64

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16 2-4 13C spectrum of TEGOH15................................................................................................ 65 2-5 DSC heating and cooling profiles for TEGOH family...................................................... 65 2-6 Annealing TEGOH15........................................................................................................66 2-7 MDSC of TEGOH15......................................................................................................... 66 2-8 Annealing TEGOH21........................................................................................................ 67 2-9 X-ray diffraction pattern for TEGOH21............................................................................ 67 2-10 IR spectrum of TEGOH15 and TEGOTr15....................................................................... 68 2-11 DSC comparisons for protected and deprotected polym ers. A) TEGOTr15 and TEGOH15. B) TEGOTr21 and TEGOH21....................................................................... 68 3-1 Model for chain folding and crys tallization in ADMET a mphiphiles............................... 90 3-2 ADMET amphiphile synthesis...........................................................................................90 3-3 1H NMR spectra of monom ers 3-3a and 3-4a.................................................................... 91 3-4 13C NMR for monomers 3-3a and 3-4a.............................................................................. 92 3-5 Assignment of aliphatic resonances in the 13C NMR spectra of monomers 3-3a and 3-4a....................................................................................................................................93 3-6 Progression from monomer 4a to polym er 8a monitored by 1H and 13C NMR................. 94 3-7 FTIR of TEGOMe21 and TEGOMe21u............................................................................ 94 3-8 DSC comparison of secondary A) and pr im ary B) polymers with PEG grafts every 21st backbone carbon..........................................................................................................95 3-9 MDSC for TEGOMe21u A) and DSC annealing experim ents for TEGOMe21u and TrEGOMe21u B)...............................................................................................................96 3-10 DSC comparison of secondary A ) and pr im ary B) polymers with PEG grafts every 15th backbone carbon.........................................................................................................97 3-11 Thermo gravimetric analysis of saturated polymers.......................................................... 98 4-1 Synthesis of polyethylene with precisely placed amphiphilic branches.......................... 115 4-2 1H and 13C NMR spectra of 9,9TEGOTs (4-2)................................................................116 4-3 1H and 13C NMR spectra of 9,9TEGOPy (4-3a)..............................................................117

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17 4-4 1H and 13C NMR spectra of 9,9TEGOHex (4-3b)........................................................... 118 4-5 1H and 13C NMR spectra of 9,9TEGOC14 (4-3c)........................................................... 119 4-6 Expansion of the aliphatic regions of the 13C spectra of 9,9TEGOPy, 9,9TEGOHex, and 9,9TEGOC14 (3a-c)...................................................................................................120 4-7 Progression from monomer 4-3c to satu rated polym er 4-5c monitored by NMR...........121 4-8 DSC heating and cooling traces for TEGOPy21u (4-4a) and TEGOPy21 (4-5a). .......... 122 4-9 Absorption and fluorescence spec tra for TEGOPy21 A) and TEGOPy21u B) ............... 122 4-10 DSC heating and cooling traces for TEGOHex21u (4-4b) and TEGOHex21 (4-5b). .....123 4-11 MDSC heating traces for TEGOHex21 (4-5b)................................................................123 4-12 DSC heating and cooling traces for TEGOC1421u (4-4c) and TEGOC1421 (4-5c)......... 124 5-1 Locations chosen for deuterium labeling in TEGOMe21................................................ 134 5-2 Synthesis of deuterium labeled TEGOMe21 analogues.................................................. 134 5-3 1H NMR of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe shown for comparison...................................................................................................... 135 5-4 13C spectra of deuterium labeled 99 TEGOMe analogues. Unlabeled 99TEGOMe shown for comparison...................................................................................................... 136

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18 Abstract of Dissertation Pres ented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy ADMET AMPHIPHILES By Erik B. Berda May 2008 Chair: Kenneth B. Wagener Major: Chemistry Acyclic diene metathesis (ADMET) allows for the synthesis of perfectly linear polyolefins with precisely controlled distri bution of some exactly defined f unctional group, either within or pendant to the polymer backbone. The materials pr oduced in this fashion possess properties that are tunable synthetically, accomplished by changing the identity of the regularly appearing moiety or the frequency of its appearance. A wide range of materials have been produced in this fashion, resulting in a catalogue of polymers displaying various morphologies and material responses. The ADMET polymerization and subse quent hydrogenation strategy when applied to the synthesis of model polymers facilitates the systematic study of various structural manipulations and their re lationship to property. Here we describe the incor poration of hydrophilic pendant de fects, namely short chain polyethylene glycol branches, onto the backbone of polyethylene using ADMET polycondensation chemistry. The motivation behind th is work is to create semi crystalline materials, intentionally excluding this hydrophilic moiety from the crystal, thereby isolating the behavior of the methylene sequences between glycol branches. The immiscibility of the hydrophobic backbone and hydrophilic defects indu ces folding of the backbone about the pendant defect allowing the clustering of the PE G branches to minimizing contact between each

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19 segment. This work demonstrates that by carefully planning the iden tity of the pendant defect it can be excluded from the crystal and induced to aggregate; excluded and induced to crystallize separately, or excluded and re-included b ack into the polymer backbone crystals. The crystallization of the backbone excluding the PEG branches to the amorphous regions, or even the formation of bicontinuous PE and PEG phase s could result in a layered or channeled morphology that may find utility in advanced applications.

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20 CHAPTER 1 INTRODUCTION The Evolution of ADMET By the m id 1980s considerable advancements had been made in the field of olefin metathesis chemistry.1 This mild carbon bond forming reaction was discovered by accident in the late 1960s when researchers at Goodyear exposed a mixture of 1olefins to a combination of tungsten hexachloride and a lewis acid with the intent to find a new catalyst for the polymerization of vinyl olefins.2, 3 Instead of high polymer the re search team observed a complex mixture of scrambled olefin products. The mech anism of this reaction, first proposed by Yves Chauvin4 in 1971 and later confirmed by Thomas Katz5 in 1975, involves the 2+2 cyclo addition of an olefin to a metal carben e to form a metallocyclobutane, followed by a 2+2 cyclo reversion to yield a new olefin and metal carbene. A majo rity of the research in the years to follow involved the development of stable metal car benes that could facilitate this useful transformation, which has become an indispensable tool to the synthetic organic chemist (Figure 1-1).1, 6 This reaction was used from its inception in th e synthesis of polymers. Despite the lack of well defined catalyst systems, a large volume of work had been produced by the mid 80s on the ring opening polymerization of strained cyclic olefins.6 This reaction, coined ROMP (ring opening metathesis polymerization) has become one of the most useful methods in the fabrication of functionalized polymers for use in every imaginable application. Although it was proposed early on that this reaction could also be used in the polycondensation of a linear diolefin, it wasnt until 1987 when the first st udy proving the feasibility of this concept appeared.7 In this report the Wagener Group at th e University of Florida attempted the polymerization of 1,9 decadiene using an ill defi ned tungsten hexachloride /lewis acid mixture,

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21 resulting in viscous oil and an intractable solid. Monitoring the di sappearance of terminal olefin signal via13C NMR and IR confirmed that the po lymerization had occurred. Since any polycondensation requires that the reaction involved proceeds quantit atively, the self metathesis of styrene to stilbene was attempted as a test reaction. The isolated product in this case was polystyrene, rather than stilbene, due to the cationic polymerization of styrene initiated by the lewis acid present in the ill defined catalyst syst em. The authors were quick to realize that while the concept was feasible, a well defined metal car bene catalyst would be necessary to prevent this detrimental side reaction.7 Fortunately, excellent progress was being made in catalyst de sign at this time. Professor Wagener was so excited by the outlook for this r eaction that he called Richard Schrock at MIT and Bob Grubbs at Cal Tech to request assistance in the area of well defined catalysts and give this acyclic diene metathesis (ADMET) a second try. Armed now with the right carbene for the job, the Wagener group successfully synthesized stilb ene from styrene in quantitative yields and reported the first viable ADMET of 1,9 decadiene to polyoctenamer.8 Examples of well-defined metal carbene metathesis catalysts are shown in Figure 1-3. It was obvious even in the initial ADMET report that this reacti on could have utility in the fabrication of unique structures.7, 8 Virtually any moiety that can be functionalized with two olefins could potentially beco me an ADMET monomer. Not surp risingly early efforts in the Wagener group involved the synthesis of a variety of functionalized polymers using this chemistry (what could R be). As metathesis catalysts became increasin gly robust and tolerant of functional groups the number of moieties that could be used in this reaction in creased and the library of ADMET polymers grew considerably. Simultaneously, research on the mechanism of this reaction ensued (Figure 14). By attacking ADMET from both practical and fundamental

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22 aspects the Wagener research group was able to carve a niche in the ol efin metathesis story. Several review articles have been published on this topic.9-11 More recently research in the Wagener group has moved specifically towards the study of precise structure (Figure 1-5) In particular, ADMET has the unique ability of producing structures that mimic copolymers of ethylene and vinyl comonomers.9-20 These ethylene based copolymers are typically made using chain pr opagation techniques, which are subject to uncontrollable side reactions that create unwanted defects. These defects in turn have adverse effects on polymer performance.9 Perfectly linear defect free model polymers can be created using ADMET. This is accomplished by synthesi zing a symmetrical terminal diene with a pendant functional group, polymerizing, and exhaustively hydrogena ting the resulting unsaturated polyolefin backbone, allowing defects to be intr oduced in a controlled manner. Knowing exactly what the identity of this de fect is and where it occurs along the backbone provides a systematic way to study this aspect of structure-property in et hylene based materials.9 This chapter describes the evolution of this study. Research on various materials from linear polyethylene free of defects, th rough the addition of halogen atoms and alkyl branches of increasing size has displayed th at not only do the precise st ructures created using ADMET possess unique properties, but that these proper ties are highly controllable. The library of polymers that has been created in this fashion and the information these polymers have provided about structure and property have led us to a new frontier: synthesi s of precisely tunable polyolefins for advanced applications. For simplic ity of discussion, the polymers described in this introduction will follow a systematic nomencl ature: the identity of the pendant moiety is named first, followed by its frequency of its a ppearance along the polyeth ylene backbone (Figure 1-6).

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23 Linear ADMET Polyethylene Unbranched, or perfectly linear, polyethylene is of considerab le in terest, particularly for studying the behavior of this hom opolymer during crystallization. Much of this work has been conducted on large n -paraffins (monodisperse PE oligomers) up to 390 carbons long, since defect free high-molecular weight PE is an elusive goal. While small molecule paraffin compounds allow in-depth study of structurally perfect model mate rials, end group concentration becomes a problem and leads to irregularities wh en trying to extrapolat e morphological behavior to a macromolecular system. The methyl endgroups present in n-paraffins are regarded as defects that hinder crystallization. Polymer chains up to millions of grams per mol, on the other hand, possess an infinitesimal number of methyl end groups relative to backbone carbons, and comparisons between these two systems can lead to ambiguous results. The synthesis of linear ADMET PE is important in this work to prove that the structures created are indeed effective as models of the commodity materials they mimic. Perfectly linear ADMET is prepared via the polymerization of 1,9 decadiene followed by saturation of the product polyoctenamer with hydrog en. While high molecular wei ght samples exhibit thermal behavior similar to that of high density polye thylene, molecular weights of products can be controlled by regulating reaction time, temperature, and the mono mer/catalyst ratio affording a family of ADMET PE polymers with varied thermal responses. Despite the relatively low molecular weight (between 2000 and 15000 g/mol) for some ADMET PEs, these polymers all display sharp DSC melting transitions above 130 C (Table 1-1). While the peak melting point increases with increased molecular weight, the polymer of Mn = 15,000 shows a peak melt of 134 C, exactly that of high density polyethylene. It is evident based on th is work that beyond the

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24 molecular weight threshold of Mn = 15,000 ADMET polymers can e ffectively model analogous commercial materials. Model Polyolefins with Precisely Placed Halogen Atoms ADMET pol yolefins with precisely placed halogen atoms (Figure 1-7) provide a unique system for studying crystallization and melti ng behavior of precision polyolefins. By synthesizing polymers decorated with fluorine, chlorine, and bromine the effect of this systematic increase in pendant defect si ze can be probed. Four separate studies13, 14, 16, 21 were conducted on this class of materials. In the firs t the static methylene se quence length between defects was held constant (18 backbone carbons) and the defect identity altered.16 In the other three the defect was held consta nt (fluorine, chlorine, or bromine) and the distance between defects altered.13, 14, 21 In the first study it was found, not su rprisingly, that w ith the increased defect size came a decrease in melting temperature and enthalpy.16 When the defect identity was held constant melting temperature and enthal py decreased with decreasing distance between defects,13, 14 the notable exception being the fluorin e containing polymers which all have approximately the same melting temperature de spite differences in defect distribution.21 Table 12 summarizes the DSC data for the precise halogenated polyethylenes. Precise Fluorine Placement. Regardless of branch dist ribution the m elting points of ADMET polymers containing precisely placed fluorine atoms are consistent with what is witnessed for linear ADMET PE, evidence that the orthorhombic crystal structur e of HDPE is unaffected by the addition of the fluorine atom.21 This result was confirmed by WAXS. This is not surprising; considering the similarity in size between hydrogen and fluorine the steric requireme nts for housing this defect in the crystal shouldnt be significantly different. Th e melting enthalpy of this family of copolymers does however decrease with increasing fluorine cont ent. This is much more significant in the

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25 cases of F15 and F9 than in the cases of F 19 and F21. The decrease in enthalpy for the higher defect concentration is eviden ce that electronic repulsions and bond polarity, as well as sterics, play an important role in the crys tallization behavior for ADMET polymers.16, 21 Precise Chlorine Placement. The consequences for the incorporation of chlorine atom s at precise intervals along polyethylenes backbone are more severe. There is a marked decrease in melting temperature from ADMET PE and the precise fluorine family. Th ere is also a change in crystal structure, from orthorhombic to triclinic. These data show that the distribution of chlorine atoms in the crystalline and amorphous regions is uniform. Further, the lamellar thickness (estimated using atomic force microscopy) far exceeds the dist ance between defects on the backbone. This confirms that the chlorine atoms are included within the crystal. The steric requirements, however, are too severe for the orthorhombic crystal structure to remain int act. This behavior is solely a result of the uniform defect distri bution, as random analogues with similar branch content possess broadened melting profiles with higher peak melting temperatures.22 This is indicative of populations of lamella with different thicknesses, typical of copolymers with random branch distribution and quite unlike the homopolymer type crystallization and melting witnessed in ADMET systems.13, 21, 22 Precise Bromine Placement. ADMET models with p recise bromine placement represent the upper size limit for our study of halogen containing polymers, as nature resisted efforts to pr oduce iodine containing ADMET polymers. As expected, the increased size of the bromine atom results in a decrease in melting temperature and enthalpy compared with the other halogenated ADMET polymers.14 Like the precision chlorine polymers a triclinic crystal structure was assigned for the bromine containing polymers. The distribution of the brom ine atoms was uniform in both crystalline and

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26 amorphous regions like the chlorine polymers, and like the random chlorine polymers the random bromine polymers exhibited copolymer type methylene sequence selection when crystallizing.22 Based on AFM measurements, as is the case for chlorine, the bromine atom resides within the crystal. Perhaps the most inte resting feature of the precision bromine polymers is their similarity in thermal response to ADMET polymers with precise methyl branch placement (discussed in the following section) Based on these findings along with the data reported for the fluorine polymers, it appears th at defect steric requirements are the most important factor in dictating the melting point of the resulting ADMET polymer crystal. Or, more simply put: a defect is a defect, regardless of its identity.14 It could be a coffee cup! Model Polyolefins with Precise ly P laced Alkyl Branches For more than half a century studies on structure and morphology have been central to polyolefin research. Discoveries in this area have allowed for the synthesis of materials with wide range of properties and be haviors. This is exemplified in the case of poly(ethyleneco -1olefins), where the behavi or of the polymer can be greatly al tered simply by varying the content and identity of the comonomer chosen. Precise Methyl Placement: ADMET Ethyle ne Propylene (EP) Copolymers. Besides being commercially significant, EP c opolym ers can provide a general insight to the structure property relationshi p when viewed as model systems. Consider polypropylene: highly crystalline when the orientation of the pendant methyl group is highly regular (syndiotactic or isotactic), however complete ly amorphous when backbone methyl groups are randomly oriented (atactic); a simple structur al difference resulting in significantly altered behavior. Linear defect free polyethylene, the other extreme, is highly crystalline. However, this crystallinity can be disrupted by the incorporation of defects, clearly evident in the aforementioned halogen work. Between the extr emes of amorphous attactic polypropylene and

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27 highly crystalline, defect free polyethylene lie EP copolymers. Simply varying the amount and placement of the incorporated methyl defect allo ws the response of the final material to be significantly altered and ultimately controlled.9 Although numerous methods are available fo r producing model polymeric systems, ADMET modeling controls comono mer content and distribution, therefore leading to fewer ambiguities relative to other model systems when relating structure on the molecular level to macroscopic properties.9, 19, 23, 24 Polymerization of symmetrical methyl branched terminal dienes, followed by exhaustive saturation of the resultant polymer, afford these precise EP models (Figure 1-8).19 These models are named according to the frequency of the pendant defect, i.e. Me21 for a methyl branch every 21st backbone carbon, Me15 for every 15th and so on. To date Me5, Me7, Me11, Me15, Me19, and Me21 have been investigated. The syntheses of Me11 through Me21 are rather straight forward using this simple yet elegant polymerization/hydrogenation approach.19 Placing branches every 5th or 7th backbone carbon requires the synthesis of a symmetrical dien e dimer, as the corresponding diene monomers undergo ring closing metathesis rather than ADMET.24 Attempts to place methyl groups every third backbone carbon, using a diene trimer, were unsuccessful due to the placement of the methyl group in the allylic posi tion. This allylic methyl decr eases the yield of the cross metathesis reaction allowing for only the partia l oligermerization of the diene (Figure 1-9).25 The effects of branch distribu tion are clear when examining the thermal behavior of the precision EP copolymer family.19 As defect content increases melting temperature and enthalpy decrease. These precise models are semicrystal line even at branch contents high enough to render random EP copolymers completely amorphous. Not until methyl groups are placed on

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28 every 5th carbon do these precise ADMET EP copolym ers lose the ability to crystallize.24 Table 1-3 summarizes the DSC data fo r the precise methyl family. Copolymerization of ADMET EP monomers w ith 1,9 decadiene, thereby forming linear EP copolymers with random branch di stribution, has also been accomplished.23 In this study it was again found that as the branch content increa sed, over all crystallinit y as well as the melting temperatures and enthalpies decreased. In the cases of the highe st amount of branch incorporation the random materials exhibited a broad, ill de fined melting behavior quite unlike the sharp melting endotherm observed for the precise models with similar branch content. This drastic difference in the behavior between preci se and random models punctuates the effect of precise branch placement (Figure 1-10).19, 23 Me21 and Me15 have been further characteri zed by Wegner et al. using X-ray diffraction, TEM, and Raman spectroscopy to further und erstand their structure and morphology.26 TEM results indicate a lamellar thickness far exceedin g the inter branch distance along the backbone, proving that like chlorine and bromine atoms the methyl group must be included within the crystal. The diffraction work elucid ated crystal structure. This data showed that the chains pack into a triclinic lattice which allows inclusion of me thyl branches as lattice defects. Further, it was found that methylene sequences be tween defects participate in a hexagonal sublattice. In order for the chains to pack in this way the defects must be contained within plains oblique to the chain stems, leading to conformationally distorted crysta ls. This is more preval ent in the case of Me15 than in Me21 due to the greater defect cont ent, a result confirmed by Raman spectroscopy. The melting point depression witnessed is no surprise given these observati ons. Further scattering experiments and exhaustive DSC experiments pe rformed on Me21 by Wunderlich et al. lead to the same conclusion involving defects concentrat ed in planes between stacks of hexagonally

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29 packed methylene sequences; however a monoclinic lattice rather than tr iclinic was used to describe the main unit cell within which the defects planes and hexagonal sublattice resides.27 ADMET Polyolefins with La rger Alky l Defects. To further understand the morphology of thes e precise materials and probe the size limit for inclusion of defects within the crystal, ADM ET models with precisely placed ethyl, hexyl, and geminal dimethyl branches have been examined. Precise Geminal Dimethyl Placement. Precision gem inal dimethyl ADMET models (Fig ure 1-11) display the effect increasing steric bulk has on the polymers thermal behavior.20 The addition of the second methyl group when moving from Me9 to 2Me9 disrupts the polyme rs ability to pack into crystals resulting in an amorphous material for 2Me9. Extending the inter defect sequence length to 14 or 20 carbons renders the polymer semicrystalline with a depr essed melting temperature when compared to the analogous EP models. Interestingly, 2Me15 shows much less melting point depression from Me15 than does 2Me21 from Me21. Further, 2M e21 shows thermal behavior unlike either 2Me15 or any of the EP family. Exhaustive DSC studi es on this material reveal that much of this behavior is dependant on thermal history. WAXD studies show reflections associated with hexagonal, monoclinic, and triclinic packing poin ting towards polymorphism as a possible cause of this complex behavior. The melting behavior was found to be incident with the melting of eicosane (a 20 carbon n-paraffin), suggesting that crystalliz ation behavior of 2Me21 is strongly related to the branch to branch distance.27 The DSC data for this family of polymers is shown in Table 1-4. Precise Ethyl Branch Placement. Ethylene bu tene (EB) copolymers featuring pr ecisely placed ethyl branches (Figure 1-12) were the next logical step in this study; moving from two singl e carbon defects to a single two

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30 carbon defect.17 These are of particular interest as EB copolymer s are important materials commercially. Like 2Me9, Et9 is fully amorphou s. Again, extending the space between defects allows for crystallization in both Et15 and Et 21. Like the geminal dimethyl models the EB models show greatly depressed melting temperatur es when compared to the EP models. Another point of interest is the difference in the obs erved thermal behavior from both the geminal dimethyl family and the EP family. EB copolym ers exhibit bimodal melting profiles very much unlike the sharp, uniform melt exhibited by the EP family.17 WAXD investigations,17 as well as exhaustive DSC analysis27 have helped in explaining this behavior. Like 2Me21, the me lting behavior of Et21 can be corr elated with that of eicosane and is therefore very much dependant on the br anch to branch distance. The WAXD results shows some lattice expansion implying the partia l inclusion of ethyl gr oups into the crystal, however to a lesser extent than in EP21. Comparing these results for 2Me21 and Et21 imply that much of the melting behavior is attributed to crystallization of methylene sequences between defects. The bimodal melt could therefore be a result of polymorphism involving the inclusion and exclusion of these defects, or a melting and simultaneous crys tallization mechanism. In or out of the crystal, the effect of increased volume requirements of the defect when increasing the size by just one methylene unit is obvious. Table 1-5 summarizes the DSC data for the precise ethyl family. Precise Hexyl Branch Placement. ADMET Et hylene Octene (EO) models serve as LLDPE models with precise hexyl branch placement (Figure 1-13).12 These precise EO models follow a similar trend in behavior as the previously discussed families; that is with increasing branch content decreasing melting temperature and enthalpy are obs erved. It is no surprise that Hex9 is totally amorphous, as the much smaller ethyl branch is able to completely disrupt crystallinity at th is branch concentration.

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31 A semicrystalline morphology is observed for Hex15; an interesting result considering all other known EO copolymers with simila r branch content are amorphous.12 Hex21 is as well semicrystalline. The very low melting temperature ( 16 C) is indicative of very small crystallites. Interestingly the melting enthalpy of Hex21 is similar to that of Et21, which is likewise surprising considering the notable decreases in enthalpy from Me21 to 2Me21 to Et21. The melting profile of the Hex21 closely mimics that of Me21 with a single sharp melting endotherm, rather than the complex endotherms displayed by 2Me21 and Et21. One possible explanation is that the hexyl branch is of sufficient size to be completely excluded from the crystal, owing the observed behavior to the crystalliz ation of the inter defect methyl ene units. The inclusion of the branch resulting in a single crystal form as seen in Me21 is another possibility. With no scattering data available for this polymer conc lusions on whether or not the hexyl branch is included or excluded from the crystal in these precise EO models based on thermal behavior alone. Table 1-6 summarizes the DSC data for this group of polymers. Some reasonable conclusions can be drawn by comparing the DSC heating traces of Et21 and Hex21 (Figure 1-14).12, 17 The lower melting mode of th e bimodal melting endotherm for Et21 perfectly overlaps with the melting endother m for Hex21. Taking the similarity of melting enthalpies into consideration as well is seems possible that at defect sizes beyond the ethyl group the inter defect methylene sequences can crysta llize and exclude the br anch to the amorphous regions. For these larger defects it would mean that these crys tals do not organize into well defined lamella as the ADMET EPs do. It is possible that there are fewer carbons in the paraffinic crystal structure for Hex21 than for the other alkyl branched ADMET models (based on the decreased melting temperature), where the def ect itself as well as the point at which the branch connects to the backbone would be exclud ed form this crystal, creating pockets of

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32 uniform nanocrystallites randomly oriented in a matrix of amorphous hydrocarbon. This model for the crystallization of ADMET polyolef ins is illustrated in Figure 1-15. Precise Ether Placement Model polym ers with the precise placement of ether moieties along a PE backbone (Figure 1-16) represent the first exampl es of linear ethyle ne-co-vinyl ether polymers ever made.28, 29 Difference in reactivity ratios between ethylene and vinyl ethers prevented the synthesis of this type of material via chain propagation chemistry until very recently.30 These polymers differ from their alkyl branched cousins only by the ex change of the methylene unit directly off the backbone for an oxygen atom, which allows for some intriguing comparisons. Looking at the thermal behavior of OMe21 and Et21, shown in Figure 1-10, reveals a very interesting result.9 The addition of the oxygen results in a slight increase of the peak melting temperature and melting enthalpy. The melting temperature for OMe 21, like several of the previous examples, is incident with that of eicosane. As the steric requirements are roughly the same for these two polymers it can be concluded th at the polarity of the bond and the electronics of the oxygen create a favorable place to initiate a fold in the polymer backbone, allowing for a more complete crystallization of the inter def ect paraffic unit cell. The DSC da ta for this group of precision polyolefins are shown in Table 1-7. Toward Advanced Applications Precise Carboxylic Acid Placement. A fa mily of polymers with precise placem ent of carboxylic acids made using ADMET (Figure 1-18) were synthesized to model commercial analogues.31 The resulting material produced some very significant data concerni ng the morphology of ADMET polymers. One of the most interesting features of these polymers is the fact that all of the carboxylic acid groups are dimerized based on the FTIR spectra. Base d on SAXS measurements on these polymers it

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33 was found that they contain a high degree of order that corresponds directly to the inter defect distance. WAXS data confirms that the paraffi nic crystal structure is uninterrupted by the incorporation of these de fects. The melting point of COOH21, like the 2Me21, is incident with eicosane. Correlating this data confirms that the methylene sequences between acids organize into a paraffin like crystal with the dimerized carboxylic acids concentrated in defect planes, similar to what was observed for the Me21. Di ffraction experiments on a drawn sample of COOH21 provide even more compelling evidence fo r this; several concentric reflections were observed, corresponding to 1, 2, a nd 3 parallel stacks of crys tallized inter-acid methylene sequences. This behavior is in sharp contrast to that of the random analogues, again highlighting the ability of ADMET to impart unique morphol ogical features into polymeric systems by perfectly controlli ng microstructure.31 Table 1-8 summarizes the DSC data for these polymers. Precise Ionomers A fa mily of precise ADMET ionomers was exam ined by neutralizing the above carboxylic acid polymers with various amounts of zinc salt.32 As seen in the other ADMET studies presented here, these materials did not behave at all like their random counterparts. In DSC experiments the first heating trace of these ma terials resulted in liquid crystalline like thermograms due to the melting of the well ordered interdefect paraffinic structures, resulting in an LC like phase, before entering an isotropi c melt. This behavior was not repeatable on subsequent cooling and heating, implying that th e ionic clusters and carboxylic acid dimers dominate the morphology when the material is cool ed after the initial he ating cycle. Long term annealing experiments were not c onducted, however to see if the re -ordering of the inter defect methylene sequences could occur.

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34 Purpose of Study The question of whether or not large defects ar e included or excluded from the crystals of these ADMET polym ers is central to our work in the Wagener research group. While the alkyl branching work is interesting and provides insight into the unique behavior of ADMET polymers, the composition of the defect is still id entical to that of th e backbone, and therefore there remains the propensity for the inclusion of such a defect into the polymer unit cell. This dissertation describes the incorporation of hydr ophilic pendant defects, namely short chain polyethylene glycol branches, onto the backbone of polyethylene using ADMET polycondensation chemistry. The motivation in this work is to intentiona lly exclude the defect from the crystal, thereby isolating the behavior of the inter defect methylene sequences. Phase separation and self assembly of PE-co-PEG block copolymers and block oligomers is well known.31-49 However this strategy has not been applie d to precision polyolefins with any well defined goal in mind. The immiscibility of the hydrophobic backbone and hydrophilic defects should induce a specific behavior: the PE backbone chains should fo ld to allow the clustering of the PEG branches, minimizing contact between each segment. The crystallization of the backbone while excluding the PEG branches to the amorphous regions, or even the formation of bicontinuous PE and PEG phases could result in a la yered or channeled morphology (depicted by a simple cartoon in Figure 1-19) that may find utility in advanced applications such as polymer electrolytes or membrane technologies. Chapter 2 describes the synthesis of a seri es of ADMET polymers with hydroxy terminated PEG branches. A protecting group was used to en sure the absence of side reactions during monomer synthesis and polymerizat ion. The thermal behavior of the polymer with and without the protecting group was evaluated; it was found that the identity of the graft end group can significantly alter the beha vior of these polymers. Analysis of the data collected for this family

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35 revealed that the polymer backbone forms crys tallites while excluding the PEG branches to amorphous regions. Chapter 3 describes the synthesis of a series of ADMET polymers with methoxy terminated glycol branches. Methyl gro ups are small enough as not to disrupt backbone crystallization, but lack the ability for hydroge n bonding possessed by the polymers in chapter 2. Three parameters are altered in this study: the length of the PEG graft, the manner in which the branch is connected to the backbone, and the distribution of the branch along the backbone. Doing so isolates the effect all three features ha ve on the ability of the backbone to crystallize. These polymers were analyzed both before and after hydrogenation to understand the effect the site of unsaturation (essentially a defect) has on the crystallization of the backbone. Chapter 4 examines whether or not self assembly or aggreg ation of functional groups attached to the end of the PEG chains is possible. This is an important questionif this concept is proven tailoring these polymers for application has promise. First, the end of the PEG chain was labeled with a pyrene unit. Fluorescence measurements confirm excimer fo rmation and therefore th e interactions of the pyrene groups. Although this aggregation results in an increase in gla ss transition temperature relative to the corres ponding unlabeled polymer, the crysta llinity of the polymer backbone remains intact displaying that the amorphous content can be altered independently of the crystalline regions. Two different n-paraffin end groups are also st udied, the goal being to induce self assembly of the branches and thus alte r the crystallization behavior. This chapter demonstrates that by carefully plan ning the identity of the pendant defect it can be excluded from the crystal and induced to aggregate; exclude d and induced to crysta llize separately, or cocrystallized with the polymer backbone crys tals. Chapter 5 describes the synthesis of deuterium labeled polymers analogous to the materi als described in chapter three. By labeling the polymer at 3 different locations informati on about molecular motion at these points above

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36 and below the polymers glass transition and melti ng temperatures can be accessed by solid state deuterium NMR. The solid state NMR experiments themselves are, however, beyond the scope of this dissertation and are therefore not discussed.

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37 Figure 1-1: Olefin metathesis reactions Figure 1-2: The ADMET polycondensation reaction.

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38 Mo F3C F3C CF3 F3C O O Ru Cl Cl Cy3P PCy3 N N Ru Cl Cl Cy3P N N Ru Cl Cl O Schrock'sMolybdenum Catalyst Grubbs'FirstGeneration Catalyst Grubbs'SecondGeneration Catalyst GrubbsHoyveda Catalyst Figure 1-3: Well defined metathesis catalysts Figure 1-4: The ADMET mechanism

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39 R n n 1.ADMETpolymerization 2.ExhaustiveHydrogenation TheIdentityofgroupRandstaticmethylenesequencenare alteredsystematicallytoprobeeffectsonpolymerproperties R n nm R m 2n+2 Figure 1-5: ADMET polymerizati on/hydrogenation strategy for pr ecision polyolefin models Figure 1-6: Nomenclature used in this introduction for ADMET polymers Figure 1-7: Precise halogen family

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40 x n CH3 x=4,6,8,10,14,17,20 Figure 1-8: Precise methyl family m 4 m 6 partialoligimerization, nopolymerformed 1.Polymerization 2.Hydrogenation 1.Polymerization 2.Hydrogenation Catalyst nn Catalyst n=3ormore:polymerization n=2orless:ringclosingmetathesis Figure 1-9: Synthesis of ADMET EP models. S horter run lengths requ ire the use of ADMET dimmers. The use of ADMET trimers for placing groups every 3rd is complicated by the presence of the a llylic methyl groups.

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41 Figure 1-10: DSC comparison of random and precis e EP polymers with similar branch content. x n x=8,14,20 Figure 1-11: Precise geminal -dimethyl family

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42 x n x=8,14,20 Figure 1-12: Precise ethyl family x n x=8,14,20 Figure 1-13: Precise hexyl family

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43 Figure 1-14: DSC comparison of Et21 and Hex21 (data taken consecutively on the same DSC independent of references 13 and 18)

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44 planesof pendant defects planesof endgroup defects similarcrystallizati onandmeltingbehavior proposedADMET polyolefincrystal Paraffincrystal Figure 1-15: Model for the crystallization of ADMET polyolefins with larger defects Figure 1-16: Precise ether family

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45 Figure 1-17: DSC comparison of OMe21 and Et21 Figure 1-18: Precise carboxylic acid family

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46 Figure 1-19: Target morphology

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47 Table 1-1 : Effect of molecular weig ht on thermal behavior in linear ADMET polyethylene Mn Polydispersity Index (PDI) Tm (C) (peak) hm (J/g) 2400 2.4 130.7 252 7600 2.4 131.3 213 11000 1.9 132.0 221 15000 2.6 133.9 204 Table 1-2: DSC data for precise halogen family Polymer Tm (C) hm (J/g) F9 124 137 F15 124 174 F19 127 207 F21 124 205 Cl 9 41 27 Cl 15 63 87 Cl 19 72 105 Cl 21 81 11 Br9 -14 21 Br15 49 35 Br19 63 55 Br21 70 48 Table 1-3: DSC data for precise methyl family Polymer Tm (C) hm (J/g) Me5 Amorphous Me7 -60 19 Me9 -14 28 Me11 11 66 Me15 39 82 Me19 57 96 Me21 63 103 Table 1-4: DSC data for precise geminal -dimethyl family Polymer Tm (C) hm (J/g) 2Me9 Amorphous n/a 2Me15 32 40 2Me21 45 61

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48 Table 1-5: DSC data for precise ethyl family Polymer Tm (C) hm (J/g) Et9 Amorphus n/a Et15 -33 & -6 Not reported Et21 17&34 (ref 18) 48 Table 1-6: DSC data for precise hexyl family Polymer Tm (C) hm (J/g) Hex9 Amorphus n/a Hex15 -48 19 Hex21 16 53 Table 1-7: DSC Data fo r precise ether family Polymer Tm (C) hm (J/g) OMe11 -41 35 OMe15 -10 62 OMe21 40 78 OEt11 -4 66 OEt15 -33 82 OEt21 28 96 Table 1-8: DSC data for precise carboxylic acid family Polymer Tm (C) hm (J/g) COOH9 Amorphous n/a COOH15 Amorphous n/a COOH21 45 42

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49 CHAPTER 2 ADMET AMPHIPHILES: POLYETHYLENE WITH P RECISELY PLACED HYDROPHILIC DEFECTS Introduction Am phiphilic copolymers receive considerable at tention in the literature due to the vast array of compositions, morphologies, and properties available in these materials.33-40 Systems featuring hydrophilic segments, often poly(ethylen e glycol) (PEG), and lipophilic segments such as polyethylene (PE) are of interest due to their biocompatibility, propensity for phase segregation, and ability to self assemb le into higher or dered structures.33-44 Block copolymer architectures are by far the most investigated, which is not surprising as advances living polymerization techniques have f acilitated the synthesi s of numerous systems with well defined structures.35, 36, 38, 40, 41, 45-48 Amphiphilic graft copolymer architectures have received less attention, likely due to the inability to control composition and structure with the same precision available in block copolymer synt hesis. This is particularly true for PE-g-PEG systems where only a few examples exist, most of which lack st ructural control in terms of graft incorporation or distribution.42 Well defined microstructures are essential to fully understand the behavior of amphiphilic graft copolymer model systems. Acyclic diene metathesis (ADMET) polycondensation chemistry is an excellent tool to model polymeric systems that lack such structural regularity when synthesized through other means. A numb er of ethylene based copolymers have been modeled in this fashion, from simple ethylene-co-olefin systems made to mimic industrial polyethylene9 to materials inaccessible through other means such as poly(ethylene-co-vinyl ether)9, 28, 29 and so called bio-olefins.49, 50 The synthesis of PEG grafted unsaturated pol yolefins with controlled placement of PEG grafts has been previously reported.43 These polymers contained an overwhelming weight

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50 percentage of polyether, and the properties reported reflected this In that study the polyolefin backbone remained unsaturated; this site of unsaturation in the backbone repeat unit serves as a defect well known to impede the crystallization of PE.9 Recent success in controlling the crystallization behavior and morphology of polyethylene through the incorporation of pendant moieties of various size and polarity13, 14, 16, 28, 31 inspired this study, whic h investigates fully saturated versions of these PEG grafted polyethylenes. This chapter describes the synthesis of a family of polymers with short glycol chains (4 oxyethylene repeat units) attached every 9th, 15th, and 21st carbon along a backbone of polyethylene. By pr ecisely controlling structure, the relative weight percentages of PE and PEG can be va ried and the morphological effects of this architecture systematically probed. The goal is that by incorporating a pendant group that is immiscible with the PE backbone it may be pos sible to build a layered or channeled morphology that would have utility in advanced applications. The precise polymer structures have been confirmed by NMR (1H and 13C). Thermal characterization by differential scanning calorimet ry (DSC) reveals proper ties ranging from semi crystalline to fully amorphous. When the PE an d PEG content are nearly equal, the polymer contains a high degree of amorphous content, as well as crystalline regions that display variable melting behavior based on thermal history. For the case of the highest amount of polyether incorporation, the material is completely amorphous. The lowest amount of polyether incorporation results in a semicrystalline mate rial; the melting temperat ure incident with nparaffin molecules of length similar to the static methylene sequence length between PEG branches. X-ray diffraction experiments confirmed th at the crystallinity is a result of the PE backbone, which crystallizes excluding the PEG graft, creating crystalline phases of pure polyolefin dispersed in a matrix of amorphous PEG and PE phases.

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51 Experimental Section Instrumentation. All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to residual signals from CDCl3 (1H: = 7.27 ppm and 13C: = 77.23 ppm) with 0.03% v/v TMS as an internal reference. Thin layer chromat ography (TLC) was performed on EMD silica gel coated (250 m thickness) glass plates. Developed TLC plates were stained with iodine adsorbed on silica to produce a visible signature Reaction conversions and relative purity of crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR) measurements were conducted on polymer films ca st from chloroform onto KBr plates using a Bruker Vector 22 Infrared Spectrophotometer. Hi gh resolution mass spectro metry analyses were performed on a Bruker APEX II 4.7 T Fourie r Transform Ion Cyclone Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization (ESI). The XRD measurements were taken using a Philips X Pert MRD system using grazing incidence (omega=3). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA). Molecular weights and molecu lar weight distributions ( Mw/Mn) were determined by gel permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid chromatography system with an internal differe ntial refractive index detector (DRI) and two Waters Styragel HR-5E columns (10 microns PD, 7.8 mm ID, 300 mm length) at 40 C. HPLC grade tetrahydrofuran was used as the mobile phase (flow rate = 1.0 mL/minute). Retention times were calibrated against polystyrene standard s (Polymer Laboratorie s; Amherst, MA). Differential scanning calorimetry (DSC) and temperature modulated differential scanning calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid

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52 nitrogen cooling accessory calib rated using sapphire and high purity indium metal. All samples were prepared in hermetically sealed pans (4-7 mg/sample) and were referenced to an empty pan. Samples were run under s purge of helium gas. A scan rate of 10 C per minute was used unless otherwise specified. Modulated e xperiments were scanned with a 3 C per minute linear heating rate with modulation amplitude of 0.4 C and period of 80 seconds. Melting temperatures are taken as the peak of the melting tr ansition, glass transition temperatur es as the mid point of a step change in heat capacity. Annealing experiments were conducted as follows: samples were heated through the melt at 10 C per minute to erase th ermal history, followed by cooling at 10 C per minute to -150 C, heated at 10 C per minute to the annealing temperature, held isothermally for 1 hour, cooled rapidly to -150 C, and heated through the melt at 10 C per minute. Data reported reflects this final heating scan. Materials. Unless otherwise specified all reagen ts were purchased from Aldrich and used without further purification. Grubbs 1st generation catalyst was a gift from Materia, Inc. Diene tosylates 1a-c and tetra(ethylene glycol) monotrityl ether were synthesized according to the literature.17, 19, 40, 44 General Procedure for the Synthesis of Trityl Protected Tetra(ethylene glycol) Monomers Anhydrous DMF (250 m l) was cannula transfer red into an oven dried, 3 neck round bottom flask equipped with a magnetic stirrer, ga s inlet, and charged with sodium hydride (1.3 eq, 60% dispersion in mineral oil). The slurry was cooled to 0C and 1.2 equivalents of tetra ethylene glycol monotrityl ether in 30 mL of anhydrous DMF were added via syringe. Hydrogen evolution was monitored by bubbler; when gas evoulu tion ceased 1 equivalent of 1 in 30 mL of anhydrous DMF was added via syringe. The reac tion was stirred for 17 hours at 0 C and quenched by pouring into 600 mL of water. The resulting mixture was ex tracted with diethyl

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53 ether and the combined organics washed with br ine. Concentration afforded a yellow oil which was further purified by column chromatography. 2-(4-pentenyl)-6-heptenyl-1-tetra(ethyle ne g lycol) monotrit yl ether (2-2a). Column Chromatography: 55% diethyl ether 45% hexane eluent yiel ded 3.2g (55% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 9H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H) 4.98 (m, 4H), 5.82 (m 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 26.09, 30.83, 34.09, 37.86, 63.19, 70.15, 70.35, 70.44, 70.51, 70.56, 74.53, 86.28, 113.92, 126.68, 127.51, 128.48, 138.97, 143.91. ESI/HRMS: [M+NH4] + calcd for NH4C39H52O5, 618.4153; found 618.4128. Anal. (CH) calcd for C39H52O5: C, 77.96; H, 8.72. Found C, 77.91; H, 8.82. 2-(7-octenyl)-9-decenyl-1-tetra(ethylene glyco l) monotrityl ether (2-2b). Column Chromatography: 25% ethyl acetate 75% hexane eluent yielding 4.0g (60% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H) 4.98 (m, 4H), 5.82 (m, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 26.52, 28.71, 28.92, 29.70, 31.08, 33.58, 37.86, 63.09, 70.13, 70.36, 70.43, 70.50, 70.57, 74.54, 86.29, 113.90, 126.67, 127.52, 128.49, 138.98, 143.92. ESI/HRMS: [M] + calcd for C45H64O5, 684.48; found 684.4753. Anal. (CH) calcd for C45H64O5: C, 78.90; H, 9.42. Found C, 78.96; H, 9.48. 2-(10-undecenyl)-12-tridecenyl-1-tetra(ethyle ne glycol) monotrityl ether (2-2c). Colum n Chromatography 15% et hyl acetate 85% hexane eluent afforded 1.01g (34% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H) 4.98 (m, 4H), 5.82 (m, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 27.03, 29.14, 29.35, 29.71, 29.82, 29.85, 30.28 31.52, 34.01, 38.29, 63.51,

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54 70.57, 70.78, 70.86, 70.92, 70.99, 74.98, 86.71, 114.28, 127.08, 127.92, 128.90, 139.41, 144.32 ESI/HRMS: [M+NH4]+ calcd for NH4C51H76O5, 786.6031; found 786.6037. Anal. (CH) calcd for C51H76O5: C, 79.64; H, 9.96. Found C, 79.46; H, 10.03. General Procedure for ADMET Polymerizations Monom ers were dried under vacuum at 80 C for 48 hours prior to polymerization and transferred to a 50 ml round bottom flask equi pped with a magnetic stir bar. Grubbs 1st generation catalyst (300:1 mono mer catalyst ratio) was added and the flask placed under vacuum at 45 C for 4 days. Polymerizations were quenche d with ethyl vinyl ethe r (5 drops in degassed toluene), precipitated into acidic methanol to rem ove catalyst residue, and is olated as an adhesive gum. Polymerization of 2-(4-pentenyl)-6-heptenyl-1-tetra(ethylene glycol) monotrityl ether (TEGOTr9u, 2-3a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 9H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 26.09, 30.83, 34.09, 37.86, 63.86, 70.72, 71.01, 71.13, 71.27, 71.33, 75.15, 86.67, 127.14, 128.15, 129.15, 130.06 (cis olefin), 130.79 (tra ns olefin), 144.68. IR ( cm-1) 2924, 2852, 1488, 1462, 1447, 1106, 1032, 1010, 966, 745, 760, 705. GPC (THF vs. polystyrene standards): Mw = 9100 g/mol; PDI ( Mw/Mn) = 1.89 Polymerization of 2-(7-octenyl)-9-decenyl-1 -tetra(ethylene glycol) mon otrityl ether (TEGOTr15u, 2-3b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 21H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 27.40, 27.84, 29.87, 29.95, 30.32, 30.40, 30.58, 31.96, 33.25, 38.71, 63.91, 70.93, 71.16, 71.23, 71.30, 71.37, 75.32, 87.09, 127.48, 128.32, 129.29, 130.15 (cis olefin), 130.90 (trans olefin),

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55 144.71. IR ( cm-1) 2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 967, 746, 761, 706. GPC data (THF vs. polystyrene standards): Mw = 47300 g/mol; P.D.I. ( Mw/Mn) = 1.85 Polymerization of 2-(10-undecenyl)-12-tridecenyl-1-tetra (ethylene glycol) monotrityl ether (TEGOTr21u, 2-3c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H ), 1.98 (q, 4H), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 27.08, 29.49, 29.80, 29.93, 30.33, 31.62, 32.87, 38.39, 63.56, 70.58, 70.81, 70.88, 70.95, 71.02, 75.08, 86.76, 127.10, 127.95, 128.95, 130.09 (cis olefin), 130.54 (trans olefin), 144.37 IR ( cm-1) 2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 967, 746, 761, 706. GPC data (THF vs. polystyrene standards): Mw = 49900 g/mol; P.D.I. ( Mw/Mn) = 1.71 General Procedure for Parr Bomb Hydrogenation of Unsaturated Polymers Unsaturated, trityl protected polym ers were dissolved in toluene and added to a glass lined Parr bomb. Wilkinsons catalyst was added and the bomb charged with 700 psi of H2. The reaction was stirred for 3 days at room temper ature. The resulting polymers were purified by precipitation into acidic methanol to remove catalyst residue and isolated as an adhesive gum. TEGOTr9 (2-4a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 17H ), 1.98 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 26.19, 30.86, 34.14, 37.82, 63.76, 70.63, 71.05, 71.17, 71.23, 71.41, 75.21, 86.63, 127.16, 128.12, 129.21, 144.68. IR ( cm-1) 2924, 2852, 1488, 1462, 1447, 1106, 1032, 1010, 745, 760, 705. GPC (THF vs. polystyrene standards): Mw = 9300 g/mol; PDI ( Mw/Mn) = 1.63

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56 TEGOTr15 (2-4b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 29H ), 3.29 (t, 2H), 3.21 (d, 2H), 3.50-3.75 (br, 14H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 27.12, 30.03, 30.42, 31.62, 63.55, 70.57, 70.82, 70.90, 70.96, 71.03, 127.13, 127.97, 128.96, 144.38. IR ( cm-1) 2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 746, 761, 706. GPC (THF vs. Polystyrene standards): Mw = 45100 PDI (Mw/Mn) = 1.99 TEGOTr21 (2-4c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H ), 3.21 (t, 2H), 3.29 (d, 2H), 3.50-3.75 (br, 14H), 5.35 (br, 2H), 7.19-7.36 (m, 9H), 7.43 (d, 6H). 13C NMR (CDCl3): (ppm) 27.08, 29.98, 30.37, 31.62, 38.38, 63.57, 70.58, 70.82, 70.89, 70.96, 71.02, 75.02, 86.76, 127.11, 127.95, 128.95, 144.37 IR ( cm-1) 2923, 2853, 1489, 1463, 1448, 1108, 1033, 1011, 967, 746, 761, 720, 706. GPC data (THF vs. polystyrene standards): Mw = 51700 g/mol; P.D.I. ( Mw/Mn) = 1.77 General Procedure for the Removal of the Trityl Protecting Group The saturated, trityl protected polymers 4a-c were dissolved in THF, acidified with concentrated HCl, and refluxed for 5 hours. Th e resulting polym ers we re precipitated into hexane to remove triphenyl methane and dried u nder vacuum at 80 C over night to afford an adhesive, elastic gum. TEGOH9 (2-5a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 17H ), 3.29 (d, 2H), 3.50-3.75 (br, 16H). 13C NMR (d4-methanol): (ppm) 26.75, 29.57, 30.53, 31.31, 38.29, 61.08, 70.28, 70.47, 72.56, 74.42. IR ( cm-1) 3424, 2924, 2854, 1465, 1351, 1116, 886, 722. GPC (THF vs. polystyrene standards): Mw = 9500 g/mol; PDI ( Mw/Mn) = 1.57

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57 TEGOH15 (2-5b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 29H ), 3.29 (d, 2H), 3.50-3.75 (br, 16H). 13C NMR (d8-THF): (ppm) 27.93, 30.76, 31.16, 32.52, 39.49, 62.29, 71.50, 71.62, 74.09, 75.03. IR ( cm-1) 3423, 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 48700; PDI ( Mw/Mn) = 2.13 TEGOH21 (2-5c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H ), 3.29 (d, 2H), 3.50-3.75 (br, 16H), 13C NMR (CDCl3): (ppm) 27.34, 29.95, 30.35, 31.55, 38.29, 62.00, 70.60, 70.87, 72.80, 75.04, IR ( cm-1) 3422, 2923, 2852, 1463, 1351, 1114, 887, 720. GPC data (THF vs. polystyrene standards): Mw = 63200 g/mol; PDI ( Mw/Mn) = 2.19 Results and Discussion Synthesis and Structural Analysis Synthesis of these precise amphiphilic copol ymers involves well known chemistry (Figure 2-1). Diene tosylates 2-1a-c (p repared as previously described19) were coupled with the PEG branch via Williamson etherification. Tetra ethyle ne glycol (TEG) was monoprotected with the bulky trityl (Tr) group before the Williamson etherifi cation to avoid side reactions and enhance solubility in organic media. The structures of monomer 2-2a-c were confirmed by NMR (1H and 13C), HRMS, and elemental analysis. Following po lymerization the unsaturated, trityl protected polymer was fully hydrogenated using Wilkinso ns catalyst. The pr otecting group remained untouched during this reaction a nd required subsequent acidification for removal. Polymer structures 2-3a-c and 2-4a -c were confirmed by NMR (1H and 13C) and FTIR. Molecular weight data (GPC versus polystyrene standa rds) is summarized in Table 2-1.

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58 For simplicity of discussion, a systematic nomenclature is used for these ADMET amphiphilic copolymers and monomers. Monomers ar e named first by the number of methylene carbons between the terminal olefin and branch point followed by the identity of the pendant group, for example 6,6TEGOTr for structure 2-2b. Po lymers are named first for the identity of the pendant group, followed by the frequency of its appearance al ong the backbone, e.g. TEGOH15 for structure 2-5b. Unsatu rated polymers are denoted w ith the suffix u. Figure 2-2 shows the 1H NMR spectrum of 6,6TEGOTr (arbitrarily chosen as an example) with peaks assigned: trityl protecting group (7.2-7.6 ppm), terminal olefin (5.8 and 4.9 ppm), glycol protons (3.5-3.8 ppm), branch point methylene unit (3.3 pp m), methylene unit adj acent to the protecting group oxygen (3.2 ppm), allylic protons (2.1 ppm), and internal methylene protons (1.2-1.6 ppm). The progression from monomer (6,6TEGOTr) to fully saturated, deprotected polymer (TEGOH15) by 1H NMR is shown in Figure 2-3. After polymerization with first generation Grubbs catalyst the terminal olefin signals at 4.9 and 5.8 ppm in the monomer spectrum converge to one signal for internal olefin at 5.4 ppm in the spectrum of th e unsaturated, protected polymer 2-3b. Following hydrogenation, this internal olefin peak completely disappears in the spectrum of the saturated but st ill protected polymer 2-4b. Deprot ection with HCl results in the loss of trityl protecting group signa l at 7.2-7.6 ppm as seen in the spectrum for the final polymer 2-5b. The pristine structures of the fully saturated, deprotected polymers were confirmed by 13C NMR. The spectrum for polymer 2-5b is shown in Figure 2-4, only resonances predicted by the repeat unit are present confirming the absence of side reactions and structural defects.

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59 Thermal Analysis Figure 2-5 shows the differential scanning calor im etry (DSC) cycle (first cooling scan from the melt, second heating scan ) for the series of saturated, deprotected polymers. TEGOH21 is semi crystalline with a peak melting temper ature of 29 C. Decreasi ng the space between PEG grafts when moving from TEGOH21 to TEGOH15 re sults in a decrease in melting temperature from 29 C to -3 C, as well as a decrease in melting enthalpy. Both polymers exhibit glass transitions at the same temperat ure, -63 C. The marked change in the melting behavior coupled with no change in the thermal re sponse of the amorphous character implies that the crystallinity is solely a result of the PE backbone. This is punctuated by the thermal behavior of TEGOH9, where further decreasing the number of backbone car bons between grafts results in a completely amorphous material. The glass transition temper ature for TEGOH9, -65 C, is only slightly depressed from the other polymers in this series, again indicating similar amorphous character. It can be concluded when examining the whol e series that for the case of TEGOH21 and TEGOH15 the backbone of the polymer is able to form crystallites while totally excluding the PEG grafts to the amorphous regions. In the ca se of TEGOH9, the close proximity of the PEG groups along the backbone is disrupting the ability of th e backbone to order in to crystallites. All three polymers therefore must contain amorphous regions with hi gh polyether content, confirmed by the nearly identical glass transitions. Table 2-2 summarizes the presented thermal data. The melting profile of TEGOH15 is particularly interesting as it contains a second, lower temperature endothermic shoulder. Since this mate rial shows only a single sharp crystallization upon cooling this shoulder is surprising. Various annealing ex periments were conducted to further understand this behavior (Figure 2-6). Annealing just below this shoulder induces a significant increase in its intensity without altering the higher temperature endotherm. Anne aling just above the shoulder completely

PAGE 60

60 suppresses this behavior while slightly affec ting the higher temperatur e endotherm. Annealing first above, then below induces the same eff ect on the high temperature peak, but also the reappearance of the lower temperature peak. Th ese annealing treatments should decrease this lower melting transition in all cases as the crystallites formed during cooling would provide the template for crystal growth. The low temperature p eak must therefore be an artifact of smaller, less stable crystallites formed after the initial cooling scan. This behavior was investigated in more de pth using temperature modulated DSC (MDSC). MDSC can provide a wealth of information on overlapping thermal transitions by separating reversible and irre versible processes.51 Based on the MDSC plot (Fig ure 2-7), crystallization is occurring simultaneously along with melting, beginning just above the glass transition temperature. PE segments that are locked in the amorphous regions upon cooling gain sufficient mobility to crystallize above Tg. As temperature increases this annealing process continues until finally a maximum melting temperature is reached and the crystallites formed on cooling melt with no simultaneous crystallizatio n occurring. The low temperature peak is therefore a result of these smaller crystallites under going an annealing process during heating, the higher temperature peak due to the melting of crystallites formed dur ing the cooling scan. Crystallization of the PEG grafts can be ruled out as this phenomenon is not witnessed in the other polymers of this series. Similar behavior is witnessed when a nnealing experiments are conducted on TEGOH21. Annealing at room temperature for several days TEGOH21 results in an increase in peak melting temperature, resulting in a melt that is incident with n-paraffin molecules with lengths similar to the static methylene sequence length between grafts (Figure 2-8). This result provides more compelling evidence that the crystallinity witnesse d in these materials is wholly due to the PE backbone.

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61 Although thermal analysis can provide excellent information on the dynamic crystallization behavior, it provides no informa tion on the structure of the crystallites formed. The thermal data strongly suggests that the PEG gr aft exclusion model is correct. To be certain TEGOH21 was studied by x-ray diffraction. TE GOH21 was chosen over TEGOH15 because its melting temperature allows for measurements to be taken at room temperature. The diffraction pattern of TEGOH21 is shown in Figure 2-9. A single diffraction is seen at 2 = 21.6, which lies in between the known diffraction patterns for orthorhombic paraffins27 and the (100) h reflection at 2 =20.5 for hexagonal polyethylene.52 This implies a contract ed hexagonal unit cell tending towards the paraffinic orthorohombic unit cell, almost identical to the results obtained by W underlich et. al. for poly(octedecyl acrylate),27 also in agreement with Wegners26 assessment of precise alkyl branched polyethylenes prepared by ADMET wher e the methylene sequences between branches organize into a hexagonal sub lattice within a triclinic unit cell. By correlating the XRD and DSC results obtained for these ADMET amphiphiles it can be concluded that the PE backbone is indeed forming crystallites and excluding th e glycol grafts to the amorphous regions. The terminus of the PEG graft seems to play an extremely important role in this unique behavior. Clustering of the PEG grafts, likely fo rming a pure polyether phase is evident by the broad hydrogen bonding peak in the IR spect rum for these polymers (Figure 2-10). Replacing the hydroxyl end group with the bul ky trityl protecting group when going from TEGOH15 to TEGOTr15 disrupts all crystallinity and increases the glass transition temperature by 30 C (Figure 2-11A). The results are sim ilar when moving from TEGOH21 to TEGOTr21; in this case crystallization is not totally disr upted, but it is significantl y hindered as noted by a decrease in melting temperature and enthalpy (Figure 2-11B). At this poin t it is unclear whether

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62 the lack of hydrogen bonding, the shear steric bulk of the trityl group, or a combination of both are responsible for the difference in behavior between the TEGOH and TEGOTr series. Conclusions In summ ary, amphiphilic PE-g-PEG copolymer models with precisely defined structures can be synthesized via metathesis polycondensati on chemistry; thermal data suggest that the PE backbones crystallize excluding the PEG graft, a result that is confirmed by x-ray diffraction. Thermal history has a significant effect on behavior of these materials. Th e identity of the graft end group clearly plays an important role in the morphology of such systems; the copolymer can be made semicrystalline or rendered comple tely amorphous simply by altering this group. The following chapter describes the effects of changi ng the size of the PEG graft and the manner in which it is connected to the bac kbone. Methoxy terminated PEG chains are examined to rule out hydrogen bonding or end group steric requirements as the cause of the behavior witnessed in this chapter. The effect of backbone saturation is also evaluated.

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63 OTs nn O nn OTr 4 O nn OTr 4 m O nn OTr 4 m O nn OH 4 m i ii iii iv1 2 3 4 5n=3(a) 6(b) 9(c) Figure 2-1: Polymer Synthesis. i: NaH, DMF, tetra ethylene glyc ol monotrityl ether; ii: Grubbs 1st generation, 45C, vacuum; iii: Wilkinsons Catalyst, toluene, H2 700psi; iv: THF, HCl. Figure 2-2: 1H NMR spectrum of 6,6TEGOTr.

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64 Figure 2-3: Progression of monomer (6,6TEGOTr) to polymer (TEGOH15) monitored by 1H NMR.

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65 Figure 2-4: 13C spectrum of TEGOH15. Figure 2-5: DSC heating and c ooling profiles for TEGOH family.

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66 Figure 2-6: Annealing TEGOH15. Figure 2-7: MDSC of TEGOH15

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67 Figure 2-8: Annealing TEGOH21 Figure 2-9: X-ray diffrac tion pattern for TEGOH21.

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68 4000350030002500200015001000500 20 30 40 50 60 70 80 90 100 % transmittance (cm-1) TEGOH15 (lower curve) TEGOTr15 (top curve) Figure 2-10: IR spectrum of TEGOH15 and TE GOTr15 (arbitrarily chosen as examples) showing clear hydrogen bonding stretch at ~ 3500 cm-1 in 2-5b but absent in 2-4b. A B Figure 2-11: DSC comparisons for protected and deprotected polymer s. A) TEGOTr15 and TEGOH15. B) TEGOTr21 and TEGOH21.

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69 Table 2-1: Molecular weight data for polymers described in chapter 2. Polymer Mn a (kg/mol) Mw a (kg/mol) PDIb TEGOTr9u 4.8 9.1 1.89 TEGOTr15u 25.6 47.3 1.85 TEGOTr21u 29.2 49.9 1.71 TEGOTr9 5.7 9.3 1.63 TEGOTr15 22.7 45.1 1.99 TEGOTr21 29.2 51.7 1.77 TEGOH9 6.1 9.5 1.57 TEGOH15 22.9 48.7 2.13 TEGOH21 28.8 63.2 2.19 a GPC vs. polystyrene standards; b Mw/Mn Table 2-2: DSC data for polymers described in chapter 2. Polymer Tg (C)) Cp (J/gC) Tm (C) Hm (J/g) Tc (C) Hc (J/g) TEGOH9 -65 .73 n/a n/a n/a n/a TEGOH15 -63 .28 -3 19 -34 21 TEGOH21 -63 .26 29 36 20 36

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70 CHAPTER 3 PROBING THE EFFECTS OF PENDANT B RANCH LENGTH, DISTRIBUTION, AND CONNECTIVITY IN ADMET AMPHIPHILES Introduction The m anipulation of morphology via synthetic control over microstructure spearheads research in polymer chemistry. The design of novel materials for advanced applications and the study of commodity materials to improve commerc ial products both requir e an understanding of the relationship between structur e and material behavior. Acyc lic diene metathesis (ADMET) has been utilized extensively for the modeling of polymeric systems,9-11 where linear, defect-free polymers produced by this method serve as pristine models of commercial materials or as novel materials for advanced applications.13, 14, 31, 49, 53, 54 Research in this area has shown that imparting these materials with such structural regularity results in behavior unique to this class of polymers.9, 12, 13, 31, 53 A recent area of effort in our laboratory has b een the synthesis of polyethylene with precise placement of hydrophilic branches. Although these polymers resemble traditional amphiphilic graft copolymers, there are a number of notab le differences. First, ADMET amphiphiles possess a perfectly uniform distribution of hydrophilic grafts (polyethylene glycol, PEG) along a hydrophobic (polyethylene, PE) backbone, architect ure which is typically inaccessible for PEgPEG systems.39, 42, 55 The distance between branches (14 and 20 backbone carbons apart in this study) is tunable synthetically by altering the si ze and symmetry of the diene monomer. Second, the length of the graft is preci sely defined, thereby differing fr om traditional amphiphilic graft copolymers.39, 42, 55, 56 Precise placement of hydrophilic branches on the hydrophobic backbone induces a phase separated morphology that may be desirable in advanced applications. Our recent synthesis of hydroxyl terminated te tra ethylene glycol grafted PE was the first to demonstrate such morphological control.15 In that study we concl uded that the polyethylene

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71 backbone crystallized by excluding the PEG branch based on thermal and structural investigations.15 We believe for this to occur, the PEG br anch must be inducing a fold in the PE backbone, thereby allowing for the clustering of the branches and allowing the backbone to form small, isolated paraffin like crystallites (Figure 3-1). While the domain sizes that would result from this model are quite small in comparison to other amphiphilic PEco -PEG block and graft copolymer systemes,33, 38, 39, 42, 55, 57 this behavior is well docu mented for alternating block oligomers44, 45, 58 of PEG and PE having blocks of similar size to the branch to branch distance and PEG graft lengths of our polymers. This chapter describes a family of polymers desi gned to test this model. First, the size of PEG branch is altered. If the crystallinity is sole ly a result of the backbone then the crystallization and melting behavior should be independent of branch length, which is indeed the case. Second, if the folds in the chain are occurri ng at the site of the PE G branch then the manner in which the branch is connected to the backbone should alter the behavior as well. In this report we present polymers in which the first atom of th e branch is either a carbon (methylene group) or an oxygen atom. This alters both the sterics and el ectronics at this point in the chain thereby altering the ability of the chain to fold, a resu lt confirmed by thermal investigations. Finally, altering the architecture of the b ackbone should effect changes in the behavior according to this model. We examine this in two ways: by changing the static methylene sequence length between branches and by investigating the effect a site of unsaturation (seen as a defect) has on the crystallization and melting behavior. Both para meters prove significant in influencing the behavior of the polymers presented. The pristine nature of the monomer structures (shown in scheme 1) are confirmed by NMR (1H and 13C), high resolution mass spectrometry, and elemental analysis. Corresponding

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72 unsaturated and fully saturated polyme r structures are confirmed by NMR (1H and 13C), and FTIR. The thermal behavior is thoroughly inve stigated by differential scanning calorimetry (DSC) and temperature modulated DSC (MDSC). The thermal stability of the materials is also assessed using thermogravimetric analysis (TGA). The thermal analysis results indicate that the architecture of the PE backbone as well as the manner in which the PEG branch is connect to the backbone play an important role in the crystallization and melting behavior of these ma terials. The size of the PEG branch, however, does not affect this behavior. This provides co mpelling evidence that our model for the chains folding about the defects, as pres ented in Figure 3-1, is correct. Experimental Section Instrumentation All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to residual signals from CDCl3 (1H: = 7.27 ppm and 13C: = 77.23 ppm) with 0.03% v/v TMS as an internal reference. Thin layer chromat ography (TLC) was performed on EMD silica gel coated (250 m thickness) glass plates. Developed TLC plates were stained with iodine adsorbed on silica to produce a visible signature Reaction conversions and relative purity of crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR) measurements were conducted with a Bruker Vector 22 Infrared Spectrophotometer using polymer films cast from chloroform onto KBr plates. High resolution mass spectrometry analyses were performed on a Bruker APEX II 4.7 T Fourier Tran sform Ion Cyclotron Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization (ESI). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA).

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73 Molecular weights and molecu lar weight distributions ( Mw/Mn) were determined by gel permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid chromatography system with an internal differe ntial refractive index detector (DRI) and two Waters Styragel HR-5E columns (10 micron pa rticle diameter, 7.8 mm ID, 300 mm length) at 40 C. The mobile phase was HPLC grade tetrahyd rofuran at a flow rate of 1.0 mL/minute. Retention times were calibrated versus polystyrene standards (P olymer Laboratories; Amherst, MA). Differential scanning calorimetry (DSC) and temperature modulated differential scanning calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid nitrogen cooling accessory a nd calibrated using sapphire and high purity indium metal. All samples were prepared in hermetically sealed aluminum pans (4-7 mg/sample) and were referenced to an empty pan. Samples were run under s purge of helium gas. Scan rates of 10C/min and 3C/min were used for DSC a nd MDSC, respectively. The MDSC modulation amplitude and period were 0.4 and 80 s, respecti vely. Melting temperatures were evaluated as the peak of the melting transition and glass transi tion temperatures as the mid-point of a step change in heat capacity. Annealing experiments were conducted as follows: samples were heated through the melt to erase thermal history, cooled at 10 C per minute to -150 C, heated at 10 C per minute to the annealing temperature, held is othermally for 1 hour, cooled rapidly to -150 C, and heated through the melt at 10 C per minute. Th e reported data reflect this final heating scan. Thermogravimetric Analysis (TGA) was perfor med on a TA Instruments Q5000 IR using the dynamic high-resolution analysis mode and a tw o point Curie temperature calibration (alumel alloy and high purity nickel).

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74 Materials. Unless otherwise stated, all reagents were purchased from Aldrich and used without further purification. Grubbs 1st generation catalyst was a gift from Materia, Inc. Diene alcohols 3-1a,b and 3-2a,b and oligoethoxyp-tosylates were synthesize d according to the literature.13, 17, 59 General Procedure for the Synthesis of Methoxy Terminated PEG Grafted Diene Monomers (3-3a-d, 3-4 a-d) Anhydrous DMF (40 mL) was cannula transf erred into an oven dried, 3-neck roundbottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents of sodium hydride (60% dispersion in minera l oil). The slurry was cooled to 0C and 1 equivalent of 1 in 20 mL of anhydrous DMF was added via syringe. When gas evolution (monitored by bubbler) ceased, 1.2 equivalents of 2 in 20 mL of anhydrous DMF were added via syringe. The reaction was stirred for 17 hours at 0 C and quenched by pouring into 600 mL of water. The resulting mixture was extracted with diethyl ether and the combined organics washed with brine. Concentration afforded a yello w oil which was further purified by column chromatography. 9-(tetra (ethylene glycol) monomethyl et her)-1,16-heptadecadiene (6, 6TEGOMe2, 3-3a). Column Chromatography:40% et hyl acetate 60% hexane eluent yielding 1g (38% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H) 13C NMR (CDCl3): (ppm) 25.55, 29.08, 29.32, 28.89, 33.97, 34.16, 59.19, 68.23, 70.72, 70.84, 71.10, 72.16, 80.27, 114.35, 139.31. ESI/HRMS: [M+NH4] + calcd for NH4C26H50O5, 460.3937; found 460.4048. Anal. (CH) calcd for C26H50O5: C, 70.54; H, 11.38. Found C, 70.38; H, 11.57.

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75 12-(tetra (ethylene glycol) monomethyl ether)-1,22-tricosa diene (9,9TEGOMe2, 3-3b). Column Chromatography:25% ethyl acetate 75% hexane eluent afforded .734g (30% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m, 1H), 3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 25.63, 29.16, 29.35, 29.71, 29.79, 29.86, 30.07, 34.02, 34.19, 59.23, 68.19, 70.75, 70.83, 70.85, 71.11, 72.17, 80.35, 114.31, 139.42 ESI/HRMS: [M+NH4]+ calcd for NH4C32H62O5, 544.4936; found 544.4938. Anal. (CH) calcd for C32H62O5: C, 72.95; H, 11.86. Found C, 73.48; H, 12.12. 9-(tri (ethylene glycol) monomethyl ether)1,1 6-heptadecadiene (6,6TrEGOMe2, 3-3c). Column Chromatography: 40% ethyl acetate 60% hexane eluent yielding 1.2g (51% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.35 (s, 3H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 25.52, 29.05, 29.28, 28.84, 33.94, 34.12, 59.16, 68.18, 70.72, 70.79, 70.82, 71.06, 72.12, 80.24, 114.29, 139.28. ESI/HRMS: [M+Na] + calcd for C24H46O4 Na, 416.3734; found 421.3288. Anal. (CH) calcd for C24H46O4: C, 72.31; H, 11.63. Found C, 72.72; H, 11.64. 12-(tri (ethylene glycol) monomethyl ether) -1 ,22-tricosadiene (9,9TrEGOMe2 3-3d). Column Chromatography: 25% ethyl acetate 75% hexane eluent afforded 1.01g (34% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m, 1H), 3.35 (s, 3H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 25.56, 29.10, 29.30, 29.65, 29.73, 29.80, 30.01, 33.96, 34.13, 59.16, 68.14, 70.71, 70.77, 70.83, 71.06, 72.12, 80.27, 114.24, 139.32 ESI/HRMS: [M+ NH4]+ calcd for NH4C30H58O4, 500.4673; found 500.4676. Anal. (CH) calcd for C30H58O4: C, 74.63; H, 12.11. Found C, 74.83; H, 12.37.

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76 2-(7-octenyl)-9-decenyl-1-tetra(ethylene gl ycol) monomethyl ether (6,6TEGOMe, 3-4a). Colum n Chromatography 40% et hyl acetate 60% hexane eluent yielding 1.03g (55% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 26.90, 29.09, 29.28, 30.07, 31.48, 33.95, 38.26, 59.17, 70.55, 70.68, 70.75, 70.79, 72.81, 74.90, 114.27, 139.32. ESI/HRMS: [M+NH4]+ calcd for NH4C27H52O5474.4153; found 474.4220. Anal. (CH) calcd for C27H52O5: C, 71.01; H, 11.48. Found C, 71.12; H, 11.67. 2-(10-undecenyl)-12-tridecenyl-1-tetra (ethylen e glycol) monomethyl ether (9,9TEGOMe, 3-4b). Colum n Chromatography: 25% ethyl acetate 75% hexane eluent afforded .560g (63% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 26.92, 29.06, 29.27, 29.63, 29.73, 29.76, 30.20, 31.45, 33.94,38.22, 59.13, 70.50, 70.64, 70.71, 70.75, 72.07, 74.88, 114.21, 139.29 ESI/HRMS: [M+NH4]+ calcd for NH4C33H64O5, 558.5092; found 558.5088. Anal. (CH) calcd for C33H64O5: C, 73.28; H, 11.93. Found C, 73.14; H, 12.05. 2-(7-octenyl)-9-decenyl-1-tri(ethylene glycol ) monomethy l ether (6,6TrEGOMe, 3-4c). Column Chromatography: 25% ethyl acetate 75% hexane eluent yielding 1.02g (60% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.29 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 27.31, 29.49, 29.68, 30.47, 31.88, 34.35, 38.67, 59.52, 70.95, 71.09, 71.16, 71.20, 72.52, 75.29, 114.67, 139.70. ESI/HRMS: [M+NH4]+ calcd for NH4C25H48O4 430.3891; found 430.3954. Anal. (CH) calcd for C25H48O4: C, 72.77; H, 12.72. Found C, 72.91; H, 12.88.

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77 2-(10-undecenyl)-12-tridecenyl-1-tri (ethylene glycol) mon omethyl ether (9,9TrEGOMe, 34d). Column Chromatography: 25% ethyl acetate 75% hexane eluent afforded .1.01g (55% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 26.95, 29.09, 29.30, 29.66, 29.76, 29.79, 30.23, 31.49, 33.96, 38.26, 59.16, 70.53, 70.69, 70.75, 70.79, 70.83, 72.11, 74.91, 114.24, 139.33 ESI/HRMS: [M+NH4]+ calcd for NH4C31H60O5, 514.4830; found 514.4869. Anal. (CH) calcd for C31H60O5: C, 74.95; H, 12.17. Found C, 74.83; H, 12.33. General Procedure for ADMET Polymerizations Monom ers were dried under vacuum at 80 C for 48 hours prior to polymerization and subsequently transferred to a 50 mL round-botto m flask equipped with a magnetic stir bar. Grubbs 1st generation catalyst (300:1 monomer:catalyst ratio) wa s added and the flask was stirred under vacuum at 45 C for 4 days. Polyme rizations were quenched with ethyl vinyl ether (5 drops in degassed toluene), pr ecipitated into cold, acidic metha nol to remove catalyst residue, and isolated as an adhesive gum. Polymerization of 9-(tetra (ethylene glyc ol) monomethyl ether )-1,16-h eptadecadiene (TEGOMe15u2, 3-5a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 25.63, 27.44, 29.47, 29.90, 29.97, 32.82, 34.23, 59.21, 68.20, 70.72, 70.82, 70.84, 71.94, 72.16, 80.35, 130.04 (cis olefin), 130.50 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 88700 ; PDI ( Mw/Mn) = 1.75

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78 Polymerization of 12-(tetra (ethylene glycol) monomethy l ether)-1,22-tricosadiene (TEGOMe21u2, 3-5b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 16H) 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 25.67, 27.36, 29.46, 29.58, 29.77, 29.87, 29.92, 30.02, 30.12, 32.85, 34.22, 59.24, 68.19, 70.74, 70.83, 70.85, 71.11, 72.17, 80.38, 130.05 (cis olefin), 130.54 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 114500 ; PDI ( Mw/Mn) = 1.78 Polymerization of 9-(tri (ethylene glycol ) mon omethyl ether)-1,16-heptadecadiene (TrEGOMe15u2, 3-5c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 20H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 12H), 5.35 (m, 2H). 13C NMR (CDCl3):. (ppm) 25.63, 27.44, 29.47, 29.90, 29.97, 32.82, 34.23, 59.22, 68.21, 70.67, 70.82, 70.87, 71.11, 72.17, 80.34, 130.09 (cis olefin), 130.51 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 79500; PDI ( Mw/Mn) = 1.85 Polymerization of 12-(tri (ethylene glycol) mon omethyl ether)-1,22-tricosadiene (TrEGOMe21u2, 3-5d). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 32H), 2.01 (q, 4H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 12H) 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 25.67, 27.44, 29.44, 29.56, 29.76, 29.86, 29.91, 30.01, 30.11, 32.84, 34.22, 59.22, 68.16, 70.77, 70.82, 70.87, 71.10, 72.17, 80.36, 130.07 (cis olefin), 130.53 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 108700 ; PDI ( Mw/Mn) = 1.69

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79 Polymerization of 2-(7-octenyl)-9-decenyl-1 -tetra(ethylene glycol) mon omethyl ether (TEGOMe15u, 3-6a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 26.60, 27.02, 29.06, 29.52, 29.78, 31.16, 32.43, 37.92, 58.79, 70.15, 70.29, 70.36, 70.39, 71.72, 74.51, 129.89 (cis olefin), 130.08 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 100400 ; PDI ( Mw/Mn) = 1.74 Polymerization of 2-(10-undecenyl)-12-tridecen yl-1-tetra (ethylene glycol) monomethyl ether (TEGOMe21u, 3-6b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 27.03, 29.45, 29.76, 29.81, 29.90, 30.00, 30.32, 31.54, 32.83, 38.30, 59.22, 70.55, 70.71, 70.76, 70.80, 72.12, 74.96, 130.05 (cis olefin), 130.52 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 96200 ; PDI ( Mw/Mn) = 1.76 Polymerization of 2-(7-octenyl)-9-decenyl -1 -tri(ethylene glycol) monomethyl ether (TrEGOMe15u, 3-6c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 21H), 1.98 (q, 4H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br, 12H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 27.02, 27.09, 29.48, 29.94, 30.20, 31.59, 32.85, 38.35, 59.22, 70.58, 70.74, 70.79, 70.85, 70.87, 71.16, 74.94, 130.06 (cis olefin), 130.51 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 37200 ; PDI ( Mw/Mn) = 1.74 Polymerization of 2-(10-undecenyl)-12-tridecenyl-1-tri (ethylene gly col) monomethyl ether (TrEGOMe21u, 3-6d). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br, 12H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 27.06, 27.51 29.46, 29.78, 29.83,

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80 29.92, 30.34, 31.57, 32.85, 38.35, 59.24, 70.58, 70.75, 70.80, 70.84, 70.88, 72.16, 74.97, 130.08 (cis olefin), 130.54 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 57700 ; PDI ( Mw/Mn) = 1.72 General Procedure for the Hydrogen ation of Unsaturate d Polymers Unsaturated polymers were dissolved in dry o-xylene. p-toluenesulfonyl hydrazide (TSH) and tripropyl amine (TPA) were added with stir ring (3 equivalents each). The resulting solution was refluxed for 3-4 hours while monitoring n itrogen evolution with a bubbler. When gas evolution ceased, the solution was cooled to room temperature, an additional 3 equivalents of TSH and TPA were added, and the solution was re fluxed for another 3 hours. The solutions were then concentrated to one-half of the original volume and precipitated into cold, acidic methanol. The polymers were isolated as elastic, adhesive gums. TEGOMe152 (3-5a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 28H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 16H). 13C NMR (CDCl3): (ppm) 25.67, 29.93, 30.12, 34.22, 59.21, 68.18, 70.72, 70.82, 71.09, 72.16, 80.35. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 92200 ; PDI ( Mw/Mn) = 1.71 TEGOMe212 (3-5b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 40H), 2.01, 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 16H). 13C NMR (CDCl3): (ppm) 25.68, 29.96, 30.12, 30.12, 34.22, 59.23, 68.19, 70.74, 70.85, 71.11, 72.17, 80.38. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 127500 ; PDI ( Mw/Mn) = 1.44

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81 TrEGOMe152 (3-7c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 28H), 3.21 (m, 1H), 3.29 (s, 3H), 3.50-3.75 (br, 12H). 13C NMR (CDCl3): (ppm) 25.67, 29.93, 30.12, 34.23, 59.22, 68.19, 70.76, 70.82, 71.11, 72.18, 80.37. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 86700 ; PDI ( Mw/Mn) = 1.85 TrEGOMe212 (3-7d). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 40H), 2.01, 3.21 (m, 1H), 3.29 (s, 3H), 3.503.75 (br, 12H). 13C NMR (CDCl3): (ppm) 25.67, 29.96, 30.12, 30.12, 34.23, 59.24, 68.19, 70.74, 70.83, 70.85,70.88, 71.11, 72.18, 80.38. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 117300; PDI ( Mw/Mn) = 1.55 TEGOMe15 (3-8a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 29H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br, 16H). 13C NMR (CDCl3): (ppm) 27.08, 29.98, 30.37, 31.61, 38.37, 59.23, 70.59, 70.74, 70.81, 70.84, 72.16, 74.98. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 117400 ; PDI ( Mw/Mn) = 1.50 TEGOMe21 (3-8b). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br, 16H). 13C NMR (CDCl3): (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 59.25, 70.61, 70.76, 70.83, 70.86, 72.18, 75.03. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 146500 ; PDI ( Mw/Mn) = 1.25 TrEGOMe15 (3-8c). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 29H), 3.21 (d, 2H), 3.35 (s, 2H), 3.50-3.71 (br, 12H). 13C NMR (CDCl3): (ppm) 27.06, 29.96, 30.35, 31.59, 38.35, 59.22, 70.58, 70.74, 70.81,

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82 70.84, 72.16, 74.97. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 42600 ; PDI ( Mw/Mn) = 1.71 TrEGOMe21 (3-8d). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.35 (s, 3H), 3.50-3.75 (br, 12H). 13C NMR (CDCl3): (ppm) 27.05, 29.96, 30.35, 31.57, 38.34, 59.23, 70.58, 70.75, 70.81, 70.85, 70.88, 72.17, 74.99. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 117300 ; PDI ( Mw/Mn) = 1.55 Results and Discussion Synthesis and Structural Analysis Figure 3-2 describes the synthesis of the ADMET am phiphiles used in this study. Monomers 3-3a-d and 3-4a-d were prepared via Williamson etherification of primary and secondary diene alcohols 3-1a,b and 3-2a ,b (synthsized as previously reported)13, 17 with oligoethoxyp-tosylates.59 The use of the primary diene alcoho l places a carbon atom directly off the backbone of the resulting polymer; throughou t this report the monomers and polymers produced in this fashion will be described as primary. Using a secondary alcohol places an oxygen atom directly off the backbone, monomers and polymer produced in this fashion will be described as secondary throughout this repor t. Monomer structures were confirmed by 1H and 13C NMR, elemental analysis, and high reso lution mass spectrometry. Polymerization with Grubbs 1st generation catalyst affords the unsaturated polymers 3-5a-d and 3-6a-d, which were quantitatively hydrogenated with p -toluenesulfonyl hydrazide. Polymer structures were confirmed by 1H and 13C NMR and FTIR. Molecular weights, (Table 3-1) were measured using gel permeation chromatography (THF vs. polystyrene standards).

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83 To simplify the discussion, a systematic nomen clature was adopted for these polymers and monomers. Monomers are named with a prefix for the number of methyl ene carbons between the PEG branch and the olefin (n in Figure 3-2), followed by the identity of the branch (TEGOMe for tetra ethylene glycol (x = 4), methoxy termin ated; TrEGOMe for tri ethylene glycol (x = 3), methoxy terminated). Polymers are named first for the identity of th e branch, followed by a number indicating the frequency of the branch. Unsaturated polymer s are denoted with the suffix u. Finally, monomers and polymers made from the secondary diene al cohols 3-1a-b are given the additional suffix For example, monomers 3-3a and 3-4a are 6,6TEGOMe2 and 6,6TEGOMe, polymers 3-5a and 3-6a TEGOMe 15u2 and TEGOMe15u, polymers 3-7a and 3-8a TEGOMe15 and TEGOMe152, respectively. The slight structural differences between the primary and secondary monomers are apparent in both the 1H and 13C NMR spectra. Figure 3-3 shows the 1H NMR spectra of monomers 3-3a and 3-4a, chosen arbitrarily as examples. The signal at 3.28 ppm in the bottom spectrum, corresponding to the methylene spacer, does not appear in the 3-3a spectrum. Also, the resonance for the methine proton shifts from 1.54 ppm in the 3-4a spectrum to 3.22 ppm in the 3-3a spectrum. The olefin and glycol re gion proton signals remain mostly unchanged between the two monomers. The broad overlappi ng signal for the aliphatic protons emphasizes the limitation of 1H NMR in the structural analysis of ADMET monomers and the need for thorough 13C NMR analysis. Figure 3-4 shows the 13C NMR spectra for monomers 3-3a and 3-4a. As in the proton spectra, the 13C NMR spectra for the primary and secondary monomers show significant differences. The position of the methine carbon shif ts from 38.26 ppm in the spectrum of 3-4a to 80.27 in the spectrum of 3-3a. The resonance at 74.90 in the spectrum for 3-4a, absent in the

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84 spectrum for 3-3a, corresponds to the methylene spacer carbon. The resonance at 68.22 in the spectrum for 3-3a but absent in the spectrum of 3-4a corresponds to the first methylene carbon in the glycol branch. The symmetric nature of the gl ycol branches results in the overlapping of the remaining glycol carbon signals in both m onomers (70.50-70.75 ppm), except for the methyl endgroup carbon (59.16 ppm in both spectra) and the glycol car bon closest to the branch terminus (72.15 ppm in both spectr a, unlabeled in Figure 3-3). Expansion of the aliphatic re gion (Figure 3-5) again reveal s the effect of the slight structural variation of the methylene spacer. Monomer 3-3a shows a strong downfield shift for the methylene carbons adjacent to the central meth ine carbon when compared to 3-4a. There is also an upfield shift for the next adjacent carbons in th e spectrum for 3-3a compared to 3-4a, due again to a difference in the magnetic environm ents of the two monomers methine carbons. However, past this the resonances are consis tent for the remaining aliphatic carbons and the allylic carbons. The progression from monomer 3-4a to fully saturated polymer 38a (chosen as an example), monitored by 1H and 13C NMR, is shown in Figure 3-6. Polymerization to 3-6a results in the convergence of terminal olefin signals in the monomer spectra (4.89, 5.74 ppm in the 1H spectrum, 114.26 and 139.31 ppm in the 13C spectrum) to a single internal olefin peak for the unsaturated polymer (5.38 ppm in the 1H spectrum, 130.08 ppm in the 13C spectrum). Saturation to form 3-8a results in the complete disappearance of any olefin signal in the spectra of the final polymer. Coalescence of several individual backbone carbon peaks into a single peak, due to the symmetric nature of the repeat unit, highlights the ability of ADMET chemistry to create pristine polymer microstructures. The appearance of only the resonances predicte d by the repeating unit confirms the absence of side reactions or structural irregularities.

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85 Typically, the quantitative hydrogenation of ADMET polymers is confirmed using FTIR by the absence of the out-of-plane CH wagging vibrational mode at 967 cm-1. This also occurs with this family of polymers. However, a co mbination of NMR and IR is needed, because the signal at 967 cm-1 is complicated by overlapping polyether stretches, which prevent baseline resolution (Figure 3-7). However, the IR spectra serve to verify the absence of moisture in the polymer films (no hydrogen bonding seen). This result helps confirm the interpretation of the DSC data (discussed in the subsequent section), wh ich indicate that the thermal behavior is due to the bulk morphology of the polymer and is not a result of moisture co ntent in the polyether phase. Thermal Analysis Previous ADMET studies have shown that both melting temperature and melting enthalpy decrease as the size of the pendant moieties increases.10 Interestingly, this trend is not observed in the series of polymers described here. The tri ethylene glycol and tetra ethylene glycol grafts show nearly identical peak melting temperatures and enthalpies when the branch distribution is held constant (3-8a,c; 3-7a,c; 3-6b,d; 3-8b,d; 3-7 b,d). This is compelling evidence that the model presented above is correct, as the length of the graft doesnt alter the behavior of the crystallizing backbone. Noticeable differences in glass transiti on between the tri ethylene glycol and tetra ethylene glycol grafts support this model. Referring to Figure 3-8, which shows DSC plots for polymers with tri ethylene glycol and tetra ethylene glycol grafts, in all cases th e longer graft results in a higher amorphous content a nd a more distinct glass transition. There are also remarkable differences in the thermograms for the saturated and unsaturated polymers. Comparing the melting temperatures in Table 3-2 for the unsatur ated polymers to the values for the saturated analogues (3-6b and 3-8b, 3-5b and 3-7b, 3-6d and 3-8d, 3-5d and 3-7d), differences of more than 30 C are observed, but the Tgs remain essentially unchanged, an

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86 indication that only the crystall ine region (i.e., the PE backbone) is affected by the degree of unsaturation and not the amorphous part. This once again supports our crys tallization model: the internal olefin acts a defect witch interrupts the all trans configurat ion of the methylene sequences between branches, t hus impeding crystallization. The differences between in thermal response de pending on the nature of the attachment of the PEG branch (primary or secondary), and especially for the unsaturated polymers, further support our model. The unsaturated primary pol ymers (Figure 3-8B) display rather complex thermograms with multimodal melting profiles, while the secondary analogues (Figure 3-8A) display a single melting peak characteristic of most ADMET polymers. The corresponding saturated polymers show a difference between primary and secondary branch attachment, albeit less significant. A decrease in melting enthalpy and a broadening of the endotherm is witnessed for the secondary polymers, indica ting a less perfectly formed crystal. This is definitive evidence that the point of branching is affecting the foldin g of the chains and ther efore the crystallization and melting behavior. The interesting melting behavior for TEGOMe2 1u (3-6b) and TrEGOMe21u (3-6d) were further investigated using MDSC and selective annealing experiments. MDSC provide increased sensitivity over conventional DSC, as well as the separation of kinetic and thermodynamic components of the total heat flow. This allo ws for the resolution of weak or overlapping transions.51, 60-62 MDSC data (Figure 3-9A), confirmed the existence of two separate melting endotherms in these unsaturatued polymers. Duri ng the dual annealing experiment we discovered that the polymers could be conditioned thermally to prefer either of these two different crystalline forms. The DSC thermograms obtained after annealing temperatures at -37C (just below the higher temperature endotherm but above the lower temperature endotherm), at -57C

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87 (just below the lower melting endotherm), and at -37C followed by -57C are shown in Figure 3-10B, (refer to Figure 3-8B for the unannealed curve). Annealing at -37C results in a marked increase in the melting enthalpy for the higher temperature transition compared to the unann ealed polymer. The lower temperature peak remains unaffected during this treatment. If th e bimodal melt were the result of a melting and recrystallization mechanism, th e lower temperature endotherm would be suppressed by this treatment, as crystallization would occur at temperatures above the melting point of these crystallites. This is not the case. Similarly, ann ealing at -57C results in an increase in the melting enthalpy of the lower temperature transiti on compared to the unannealed polymer, while leaving the higher temperature transition unaffect ed. Annealing at both te mperatures, first -37C followed -57C produces two very sharp, distin ct melting transitions. Further, the MDSC experiment shows no crystallization occurri ng simultaneously along with melting, noted by the absence of any exothermic transitions in any of the three heat flow signals. This confirms that the bimodal melt must be due to different crystallite populations and not to a melting and concurrent crystallization process. This ag ain supports our current model of small, isolated crystallites. The thermograms for the polymers with 15 carb ons between the PEG grafts are shown in Figure 3-10. When comparing the unsaturated polymers in Figure 3-10 to the unsaturated polymers in Figure 3-8 (20 carbons between branch points), it becomes clear that the site of unsaturation in the 15 family disrupts crysta llization, resulting in completely amorphous materials. The difference in the nature of the br anch attachment (primary versus secondary) is also witnessed in the 15 family, but the trend is opposite to that of the 21 family. The secondary polymers (Figure 3-10A) exhibit a sharper, more defined melt with a greater melting enthalpy compared to the primary polymers (Figure 3-10B ). The peak melting temperature however, is

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88 slightly depressed from the primary polymer, implying a thinner crysta l. The reason for the opposite trend for the 15 and 21 series is not clear at this point; however it is again evident that the nature of the attachment of the PEG plays a cr ucial role in the crysta llization of the backbone. Despite the differences in the crystallinity, the behavior of the amorphous content for each material is nearly identical for these polymers, the only exception being the tri ethylene glycol grafted polymers, which exhibit a smaller Cp than the tetra ethylene glycol grafted polymers. This is a clear indication that the amorphous regions across this entire family of polymers, which remain unaffected with significant changes in the structure of the backbone and the observed crystallinity, are primarily pol yether. The DSC data for all of the polymers discussed is summarized in Table 3-2 below. The thermal stabilities are similar for all of th e saturated polymers in this family. All are stable up to 380 C, above which a single-stage, rapid decomposition is observed (Figure 3-11). Conclusions This chapter described the synthesis of a family of PEG grafted polyethylene amphiphilic copolymers using ADMET chemistry. The graft length and graft distribution have been perfectly controlled during the synthesis of the monomers. By altering several structural parameters we have shown that the PEG branches are inducing folds in the backbone, resulting in small paraffin like crystallites composed of the methylene sequences between branches. The site of unsaturation in the backbone of the polymer plays an important role in the ability of the polymer to crystallize. Likewise, the manner in which the PEG branch is connected to the backbone changes the sterics and electronics as this fold point and alters the obs erved crystallinity. The size of the PEG branch, however, does not affect this behavior significantly. These slight variations in structure ultimately provide tunability over the propert ies of the final materials; the

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89 melting point of the resulting materials can be cont rolled over a range of 60 C, or rendered fully amorphous. Experiments involving PEG branches w ith different end groups, designed to induce interactions of the branches w ithin the amorphous phase of the polymer, are described in chapter 4.

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90 Figure 3-1: Model for chain folding and crystallizati on in ADMET amphiphiles. OH OH O O O O nn n n n n n n x x O O O O n n n n x x m m O O O O n n n n x x m m3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8n=6,x=4(a) n=9,x=4(b) n=6,x=3(c) n=9,x=3(d) i ii iii"Secondary" Monomers andPolymers "Primary" Monomers andPolymers Figure 3-2: ADMET amphi phile synthesis. i: NaH, DMF, TsO(CH2CH2O)xCH3; ii: Grubbs 1st generation catalyst, 45 C, vacuum; iii: TSH, TPA, o-xylenes 140 C.

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91 Figure 3-3: 1H NMR spectra of monomers 3-3a and 3-4a.

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92 Figure 3-4: 13C NMR for monomers 3-3a and 3-4a.

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93 Figure 3-5: Assignment of a liphatic resonances in the 13C NMR spectra of monomers 3-3a and 34a.

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94 Figure 3-6: Progression from monome r 4a to polymer 8a monitored by 1H and 13C NMR. Figure 3-7: FTIR of TEGOMe21 and TEGOMe21u

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95 Figure 3-8: DSC comparison of s econdary A) and primary B) polymers with PEG grafts every 21st backbone carbon.

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96 Figure 3-9: MDSC for TEGOMe 21u A) and DSC annealing e xperiments for TEGOMe21u and TrEGOMe21u B).

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97 Figure 3-10: DSC comparison of secondary A ) an d primary B) polymers with PEG grafts every 15th backbone carbon.

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98 Figure 3-11: Thermo gravimetric analysis of satu rated polymers (arbitrary vertical offsets for clarity)

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99 Table 3-1: Molecular weight data for polymers described in chapter 3 Polymer Mn a (kg/mol) Mw a (kg/mol) PDIb TEGOMe15u (3-6a) 62.7 100.4 1.60 TrEGOMe15u (3-6c) 21.4 37.2 1.74 TEGOMe15u2 (3-5a) 50.7 88.7 1.75 TrEGOMe15u2 (3-5c) 42.9 79.5 1.85 TEGOMe15 (3-8a) 78.1 117.4 1.5 TrEGOMe15 (3-8c) 24.9 42.6 1.71 TEGOMe152 (3-7a) 53.9 92.2 1.71 TrEGOMe152 (3-7c) 46.8 86.7 1.85 TEGOMe21u (3-6b) 54.8 96.2 1.76 TrEGOMe21u (3-6d) 33.5 57.7 1.72 TEGOMe21u2 (3-5b) 64.1 114.5 1.78 TrEGOMe21u2 (3-5d) 64.1 108.7 1.69 TEGOMe21 (3-8b) 117.2 146.5 1.25 TrEGOMe21 (3-8d) 41.1 70.3 1.71 TEGOMe212 (3-7b) 87.9 127.5 1.44 TrEGOMe212 (3-7d) 75.6 117.3 1.55 a GPC vs. polystyrene standards; b Mw/Mn Table 3-2: DSC data for polymers described in chapter 3 Polymer Tg (C) Cp (J/gC) Tm (C) Hm (J/g) Tc (C) Hc (J/g) TEGOMe15u (3-6a) -80 1.0 n/a n/a n/a n/a TrEGOMe15u (3-6c) -81 1.0 n/a n/a n/a n/a TEGOMe15u2 (3-5a) -81 1.0 n/a n/a n/a n/a TrEGOMe15u2 (3-5c) -81 0.9 n/a n/a n/a n/a TEGOMe15 (3-8a) -76 0.5 -9 21 -36 27 TrEGOMe15 (3-8c) -70 0.2 -6 24 -36 32 TEGOMe152 (3-7a) -76 0.4 -19 31 -28 31 TrEGOMe152 (3-7c) -74 0.3 -18 40 -29 38 TEGOMe21u (3-6b) -76 0.3 -38 18 -46 17 TrEGOMe21u (3-6d) -76 0.3 -41 22 -49 23 TEGOMe21u2 (3-5b) -76 0.4 -21 21 -37 22 TrEGOMe21u2 (3-5d) -70 0.3 -20 20 -36 22 TEGOMe21 (3-8b) -74 0.4 15 44 7 43 TrEGOMe21 (3-8d) -74 0.2 14 45 8 45 TEGOMe212 (3-7b) -71 0.3 12 45 -1 45 TrEGOMe212 (3-7d) -65 0.2 13 50 -1 50

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100 CHAPTER 4 INDUCING PENDANT BRANCH SELF AS SE MBLY IN ADMET AMPHIPHILES Introduction It is well understood that highl y regular m acromolecular structur es result in predictable and controllable behavior. This is especially true with amphiphilic copolymers, for which minor alterations in structure can i nduce a broad range of responses in the bulk and in solution.63-67 The amount of research on the synthesi s and self assembly of amphi philic block copolymers alone is remarkable.35, 37, 41, 46, 67-69 Living radical,37, 70 cationic,36, 41 anionic,71 and even metathesis72 polymerizations have been extens ively utilized in creating well defined structures that can self assemble to form interesting and useful morphologies. The use of acyclic diene metathesis (ADMET) to create highly regular, precisely defined structures is also well known.9-11 These materials, while often structurally related to copolymers made via chain copolymerization of ethylene an d vinyl comonomers, possess properties that set them apart as a completely separate class of materials.9, 12-14, 16-19, 28, 31, 53 These properties are highly tunable with minor structural alterations, imparted during the synthesis of the symmetrical terminal diolefin monomer. Two parameters are generally altered: the id entity of the pendant functional moiety and the static methylene se quence length between th is functional group and the terminal olefin. When the pendant moiety is a methyl group, systematically changing the methylene sequence length from branches every 7th carbon to branches every 21st carbon results in a control of melting poi nt over a range of 200 C.19, 24 Likewise, alteration of the pendant group size and polarity allow tunability of the properties when the methylene sequence length is held constant. In all ADMET copolymers observed previously, an increase in defect size results in a systematic decrease in melting temperature.13, 14, 18

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101 The previous chapters described the use of ADMET to synthesize a family of amphiphilic graft copolymers with polyethylene (PE) bac kbones and hydrophilic polyethylene glycol (PEG) branches. By combining the structural regularity available with ADMET and the ability of amphiphiles to phase separate and self assemble we have created semicrystalline materials in which the PE backbone crystallizes, forming pure hydrocarbon crystallites excluding the polyether branches.15 This chapter describes th e expansion of this area of research by altering the pendant PEG chain end group to create copoly mers with PE backbone s and AB amphiphilic grafts. Two of the polymers reported have the Ag-(Bb-A) motif, where an oligoethylene chain is affixed to the end of the PEG branch direc tly attached to the PE backbone. The third has a pyrene group attached to the end of the PE G chain. Labeling in the fashion allows the aggregation of these graft end groups to be examined using fluorescence measurements. To assess the influence of these pendant groups on the PE backbone accurately, the distance between pendant groups was kept constant in this chapter. A 21-carbon distance between pendant branches was chosen to ensure the cr ystallization of the backbone because previous ADMET polymers with this functional group distribution have always been semicrystalline.9-11 All monomer and precursor structures were confirmed by 1H and 13C NMR, elemental analysis and high resolution mass spectrometry. The structures of the corresponding polymers were confirmed by 1H and 13C NMR, and FTIR. Differential Scanning Calorimetry (DSC) and temperature modulated DSC (MDSC) were used to study the behavi or of these materials in the bulk. The observed thermal behavior indicates th at the three materials have very different morphologies. Affixing the PEG branch with a pyrene end group results in the complete exclusion of the pendant moiety from the crys tal, simultaneously induc ing their aggregation. Changing the end group to an n-he xyl chain results in crystalli zation of the pendant branch

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102 separately from the PE backbone. Exte nding this olgioethylene chain from n-hexyl to n tetradecyl allows the pendant moiety to extend ba ck into the polymer crystal, thereby increasing the melting point compared to the polymer with the 6-carbon terminus. The inclusion of the tetradecyl group into the crystal and resultant in crease in melting point compared to the other materials presented here is significant becau se it breaks the usual trend for ADMET polymers, which show a decrease in melting point and me lting enthalpy with increasing pendant group size. Experimental Section Instrumentation All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to residual signals from CDCl3 (1H: = 7.27 ppm and 13C: = 77.23 ppm) with 0.03% v/v TMS as an internal reference. Thin layer chromat ography (TLC) was performed on EMD silica gel coated (250 m thickness) glass plates. Developed TLC plates were stained with iodine adsorbed on silica to produce a visible signature Reaction conversions and relative purity of crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR) measurements were conducted with a Bruker Vector 22 Infrared Spectrophotometer using polymer films cast from chloroform onto KBr pl ates using High resolution mass spectrometry analyses were performed on a Bruker APEX II 4.7 T Fourier Tran sform Ion Cyclotron Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization (ESI). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA). Molecular weights and molecu lar weight distributions ( Mw/Mn) were determined by gel permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid chromatography system with an internal differe ntial refractive index detector (DRI) and two

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103 Waters Styragel HR-5E columns (10 micron pa rticle diameter, 7.8 mm ID, 300 mm length) at 40 C. The mobile phase was HPLC grade tetrahyd rofuran at a flow rate of 1.0 mL/minute). Retention times were calibrated versus polystyrene standards (P olymer Laboratories; Amherst, MA). Differential scanning calorimetry (DSC) and temperature modulated differential scanning calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid nitrogen cooling accessory calib rated using sapphire and high purity indium metal. All samples were prepared in hermetically sealed pans (4-7 mg/sample) and were referenced to an empty pan. Samples were run under s purge of helium gas. A scan rate of 10 C per minute was used unless otherwise specified. Modulated e xperiments were scanned with a 3 C per minute linear heating rate with modulation amplitude of .45 C and period of 30 seconds. Melting temperatures are taken as the peak of the melting tr ansition, glass transition temperatur es as the mid point of a step change in heat capacity. Materials Unless otherwise stated, all reag ents were purchased from Aldrich and used without further purification. Grubbs 1st generation catalyst was a gift from Materia, Inc. Diene alcohol 4-1 was synthesized as previously reported.17 Synthesis of 2-(10-undecenyl)-12-tridecenyl-1-tetra(ethylene glycol)p -tosylate (4-2). Anhydrous DMF (30 mL) was cannula transf erred into an oven dried, 3-neck roundbottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents of sodium hydride (60% dispersion in minera l oil). The slurry was cooled to 0C and 1 equivalent of 4-1 in 20 mL of anhydrous DMF was added via syringe. When hydrogen gas evolution (monitored by bubbler) c eased, the solution was cannula transferred into a well-stirred flask containing 4.5 equivalents of tetraethylene glycol di-p-tos ylate in 50 mL of anhydrous

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104 DMF. The reaction was stirred for 17 hours at 0 C and quenched by pouring into 300 mL of water. The resulting mixture was extracted with diethyl ether and the combined organics washed with brine. Concentration afforded a yello w oil which was further purified by column chromatography, 30% ethyl acetate 70% hexane eluent, yielding 1.5g (52%) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 2.42 (s, 3H), 3.29 (d, 2H), 3.50-3.75 (br, 15H), 4.18 (d, 2H), 4.98 (m, 4H), 5.82 (m, 2H), 7.31 (d, 2H), 7.79 (d, 2H). 13C NMR (CDCl3): (ppm) 21.82, 27.01, 29.15, 29.35, 29.70, 20.80, 29.83, 30.28, 31.55, 34.00, 38.32, 68.89, 69.39, 70.57, 70.74, 70.79, 70.80, 70.88, 70.97, 75.01, 114.28, 128.18, 129.99, 133.33, 139.43, 144.92. ESI/HRMS: [M+NH4]+ calcd for NH4C39H68O7S, 698.5024; found 698.5023. Anal. (CH) calcd for C39H68O7S: C, 68.78; H, 10.06. Found C, 58.51; H, 9.95. General Procedure for Preparation of Monomers Anhydrous DMF (45 mL) was cannula transf erred into an oven dried, 3-neck roundbottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and 3 was added in 20 mL of anhydrous DMF via syri nge. When hydrogen gas evolution (monitored by bubbler) ceased, 1 equivalent of 4-2 in 30 mL of anhydrous DMF was added via syringe. The reaction was stirred for 17 hours at 0 C and quenched by pouring into 30 0 mL of water. The resulting mixture was extracted w ith diethyl ether and the combined organics washed with brine. Concentration afforded a yellow oil which was further purified by column chromatography. 2-(10-undecenyl)-12-tridecenyl-1-tetra (ethyl ene glycol) methenyl p yrene (9,9TEGOPy, 43a). Column Chromatography:30% ethyl acetate 70% hexane eluent afforded .475g (29% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.50-3.75 (br, 12H) 4.98 (m, 4H), 5.28 (s, 2H), 5.82 (m, 2H), 7.61-8.79 (m, 4H), 8.13-8.20 (m,

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105 4H), 8.37 (d, 1H). 13C NMR (CDCl3): (ppm) 26.96, 29.14, 29.35, 29.71, 20.82, 29.85, 30.28, 31.52, 34.01, 38.28, 69.72, 70.54, 70.75, 70.83, 70.87, 70.95, 72.04, 74.96, 114.28, 123.75, 124.64, 124.92, 125.36, 126.09, 127.22, 127.60, 127.83, 131.03, 131.47, 131.62, 139.43. ESI/HRMS: [M+NH4]+ calcd for NH4C49H72O5, 758.5718; found 758.5735. Anal. (CH) calcd for C49H72O5: C, 79.41; H, 9.79. Found C, 79.00; H, 9.80. 2-(10-undecenyl)-12-tridecenyl-1-te tra (ethylene glycol) mono n -hexyl ether (9,9 TEGOHex, 4-3b). Column Chromatography: 20% ethyl acetate 80% hexane eluent afforded .144g (17% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 41H), 2.01 (q, 4H), 3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 14.21, 22.78, 25.95, 26.92, 29.12, 29.33, 29.68, 29.79, 29.82, 30.26, 31.53, 31.87, 33.98, 38.31, 70.26, 70.57, 70.78, 70.81, 70.83, 71.71, 74.98, 114.25, 139.33. ESI/HRMS: [M+NH4]+ calcd for NH4C38H74O5, 628.5875; found 628.5887. Anal. (CH) calcd for C38H74O5: C, 74.70; H, 12.21. Found C, 74.84; H, 12.36. 2-(10-undecenyl)-12-tridecenyl-1-te tra (ethylene glycol) mono n -tetradecyl ether (99TEGOC14, 4-3c). Column Chromatography: 20% ethyl acetate 80% hexane eluent afforded .400g (34% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 57H), 2.01 (q, 4H), 3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 13C NMR (CDCl3): (ppm) 14.29, 22.88, 26.31, 27.03, 29.16, 29.36, 29.55, 29.71, 29.82, 29.85, 29.87, 30.29, 31.57, 32.13, 34.01, 38.35, 70.29, 70.60, 70.79, 70.84, 70.86, 71.75, 75.01, 114.27, 139.40. ESI/HRMS: [M+NH4]+ calcd for NH4C38H74O5, 628.5875; found 628.5887. Anal. (CH) calcd for C38H74O5: C, 74.70; H, 12.21. Found C, 74.84; H, 12.36.

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106 General Procedure for ADMET Polymerizations Monom ers were dried under vacuum at 80 C for 48 hours prior to polymerization and subsequently transferred to a 50 mL round-botto m flask equipped with a magnetic stir bar. Grubbs 1st generation catalyst (300:1 monomer:catalyst ratio) wa s added and the flask was stirred under vacuum at 45 C for 4 days. Polyme rizations were quenched with ethyl vinyl ether (5 drops in degassed toluene), pr ecipitated into cold, acidic metha nol to remove catalyst residue, and isolated as adhesive gums. Polymerization of 2-(10-undecenyl)-12-tridecenyl-1-tetra (ethylene glyc ol) methenyl pyrene (TEGOPy21u, 4-4a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 ( q, 4H), 3.29 (d, 2H), 3.50-3.75 (br, 12H) 5.28 (s, 2H), 5.35 (m, 2H), 7.61-8.79 (m, 4H), 8.13-8.20 (m, 4H), 8.37 (d, 1H). 13C NMR (CDCl3): (ppm) 27.05, 27.46, 29.46, 29.35, 29.59, 29.78, 29.92, 30.02, 30.35, 31.57, 32.86, 38.33, 69.73, 70.54, 70.76, 70.83, 70.87, 70.95, 72.05, 74.96, 123.75, 124.64, 124.93, 125.13, 125.33, 125.38, 126.10, 127.23, 127.57, 127.60, 127.84, 129.60, 130.08 (cis olefin), 130.53 (trans olefin), 131.03, 131.44, 131.47, 131.62. IR ( cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 967, 846, 802, 721. GPC (THF vs. Polystyrene standards): Mw = 80300 ; PDI ( Mw/Mn) = 1.90 Polymerization of 2-(10-undecenyl)-12-trid ecenyl-1-tetra (ethylene glycol) mono n -hexyl ether (TEGOHex21u, 4-4b). 1H NMR (CDCl3): (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 41H), 2.01 (q, 4H), 3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 14.26, 22.83, 25.99, 27.08, 29.49, 29.83, 29.97, 30.36, 31.61, 31.91, 32.87, 38.38, 70.29, 70.60, 70.86, 71.63, 75.06, 130.09(cis olefin), 130.55 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 967, 846, 802, 721. GPC (THF vs. Polystyrene standards): Mw = 84800 ; PDI ( Mw/Mn) = 1.98

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107 Polymerization of 2-(10-undecenyl)-12-trid ecenyl-1-tetra (ethylene glycol) mono n tetradecyl ether (TEGOC1421u, 4-4c). 1H NMR (CDCl3): (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 57H), 2.01 (q, 4H), 3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 14.29, 22.88, 26.31, 27.03, 29.16, 29.36, 29.55, 29.71, 29.82, 29.85, 29.87, 30.29, 31.57, 32.13, 34.01, 38.35, 70.29, 70.61, 70.79, 70.84, 70.86, 71.76, 75.01, 130.08 (trans olefin), 130.54 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 967, 846, 802, 721. GPC (THF vs. Polystyrene standards): Mw = 61900 ; PDI ( Mw/Mn) = 1.71 General Procedure for the Hydrogen ation of Unsaturate d Polymers Unsaturated polymers were dissolved in dry o-xylene. P -toluenesulfonyl hydrazide (TSH) and tripropyl amine (TPA) were added with stir ring (3 equiv each). The resulting solution was refluxed for 3-4 hours while monitoring nitrogen evolution with a bubbler. When gas evolution ceased, the solution was cooled to room temperat ure, an additional 3 equivalents of TSH and TPA were added, and the solution was refluxed for another 3 hours. The solutions were then concentrated to one-half of the original volume and precipitated into cold, acidic methanol. The polymers were isolated as elastic, adhesive gums. TEGOPy21, (4-5a). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.50-3.75 (br, 12H) 5.28 (s, 2H), 7.61-8.79 (m, 4H), 8.13-8.20 (m, 4H), 8.37 (d, 1H). 13C NMR (CDCl3): (ppm) 27.05, 29.96, 30.02, 30.35, 31.59, 38.34, 69.76, 70.56, 70.78, 70.85, 70.87, 70.97, 72.05, 74.97, 123.75, 124.64, 124.95, 125.15, 125.33, 125.38, 126.10, 127.23, 127.57, 127.61, 127.84, 129.60, 131.05, 131.44, 131.48, 131.66. IR ( cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 846, 802, 721. GPC (THF vs. Polystyrene standards): Mw = 60400 ; PDI ( Mw/Mn) = 1.93

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108 TEGOHex21 (4-5b). 1H NMR (CDCl3): (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 49H), 3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H). 13C NMR (CDCl3): (ppm) 14.28, 22.85, 25.99, 27.07, 29.83, 29.97, 30.38, 31.58, 31.93, 38.35, 70.29, 70.60, 70.84, 70.86, 71.77, 75.02. IR ( cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 846, 802, 721. GPC (THF vs. Polystyrene standards): Mw = 79200 ; PDI ( Mw/Mn) = 1.78 TEGOC1421 (4-5c). 1H NMR (CDCl3): (ppm) 0.82 (t, 3H), 1.21-1.61 (br, 65H), 3.29 (d, 2H), 3.41 (t, 2H), 3.50-3.71 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 14.29, 22.88, 26.31, 27.03, 29.55, 29.71, 29.82, 29.87, 29.97, 30.35, 31.60, 32.13, 38.38, 70.28, 70.61, 70.86, 71.76, 75.01. IR ( cm-1) 2923, 2853, 1464, 1350, 1260, 1115, 846, 802, 721. GPC (THF vs. Polystyrene standards): Mw = 65800; PDI ( Mw/Mn) = 1.76 Results and Discussion Synthesis and Structural Analysis Figure 4-1 describes the synthesis of these un ique m aterials. First, diene alcohol 4-1 (prepared as previously described17) is attached to the PEG bran ch via Williamson etherification with tetra(ethylene glycol)di p -tosylate. Disubstitution is avoi ded using careful stoichiometry. The hydrophobic endgroup is then attached to 4-2 with a second Williamson by using the appropriate alcohol. This synthetic method is general and can potentially be applied to prepare an array of ADMET monomers and subsequent poly mers having a variety of functional groups separated from the PE backbone by a PEG spacer. M onomers 4-3a-c are polymerized in the bulk at 45 C under high vacuum using Grubbs first ge neration catalyst to afford the unsaturated

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109 ADMET polymers 4-4a-c. Subsequent hydrogenation with p-toluenesulfonyl hydr azide results in the final fully saturated polymers 4-5a-c. For simplicity, a systematic nomenclature has been adopted for these monomers and polymers. Monomers are given the prefix ,9 to indicate the number of methylene carbons between the branch and the olefin, followed by th e identity of the pendant group (TEGO for tetra ethylene glycol and either Py, Hex, or C14 for pyrene, n-hexyl or n-tetradecyl). Polymers are named first for the identity of the pendant def ect, followed by the branch frequency. Unsaturated polymers are denoted with the suffix u. For example, monomer 4-3a is named ,9TEGOPy, polymer 4-4a TEGOPy21u, and polymer 4-5a TEGOPy21. The 1H and 13C NMR spectra for 9,9TEGOTs (4-2) are shown in Figure 4-2. In the proton spectrum the tosyl end group is clearly identified by the two doublets at 7.32 and 7.72 ppm, as well as the singlet at 2.45 ppm. The triplet at 4.16 ppm corresponds to the methylene protons adjacent to the tosyl group, shifted downfield fr om the overlapping glycol proton signals which appear from 3.55 to 3.61 ppm. The doublet at 3.30 ppm corresponds to the methylene protons separating the glycol moiety from the backbone The allylic protons di splay a quartet at 2.03 ppm, the central methine carbon shows a multiplet at 1.56 ppm, and the characteristic terminal olefin peaks are seen at 4.91 and 5.80 ppm. Finally, the remaining methylene protons of the diene main chain overlap into a single broa d peak at 1.26 ppm. In the carbon spectra for 99TEGOTs the resonances for the tosy l group are seen at 144.92, 133.33, 129.99, 128.18 ppm (aromatic carbons) and 21.83 ppm (methyl carbon). Terminal olefin signals appear at 114.28 and 139.43 ppm, the methylene carbon connecting the branch to the backbone appears at 75.01 ppm, and the glycol carbons overlap from 70.58 to 70.97 pp m. The glycol carbons closest to the tosyl group appear at 68.90 ppm, the central methine ca rbon is at 38.32 ppm, and the allylic carbons

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110 are at 34.01 ppm. The remaining resonances for the internal methylene carbons appear from 27 to 32 ppm and are all individually resolv ed. This highlights the need for thorough 13C analysis in the ADMET synthesis of precise polyolefi ns, because simply investigating the 1H spectra can lead to ambiguities due to overlapping resonances. The 1H and 13C NMR spectra of 9,9TEGOPy (4-3a) ar e shown in Figure 4-3. In the proton spectrum the aromatic pyrene protons appear from 8.02 to 8.43 ppm. The methylene protons between the pyrene and glycol branch appear as a singlet at 5.30 ppm. The resonances for the glycol region, terminal olefin, allylic, and aliphatic protons re main mostly unchanged compared to the 1H spectrum of 9,9TEGOTs. The case is si milar for the carbon spectrum of 9,9TEGOPy. The aromatic pyrene carbons appear from 123.74 to 131.61 ppm, and the methylene carbon between the pyrene and glycol moieties is seen at 72.04 ppm. As in the proton spectrum, the terminal olefin, allylic, and aliphatic carbons remain mostly unchanged compared to the carbon spectrum of 9,9TEGOTs. Figures 4-4 and 4-5 show the 1H and 13C NMR spectra of 9,9TEGOHex (4-3b) and 9,9TEGOC14 (4-3c), respectively. In the proton spectra the n-hexyl and n-tetradecyl methyl end groups appear at 0.87 ppm, and the methylene pr otons adjacent to the glycol portion of the branch appear as triplets at 3.44 ppm. The rest of the n-hexyl protons overlap with the internal methylene protons of the diene main chain. The remaining resonances are unchanged as described in the previous example. The carbon sp ectra for these monomers are nearly identical except for the aliphatic regions, which are comp licated by the overlapping diene main chain and aliphatic branch carbon resonances. An expanded view of the aliphatic regions in the 13C NMR spectra of 9,9TEGOHex, 9,9TEGOC14, and 9,9TEGOPy is shown in Figure 4-6. Comparing 9,9TEGOPy to the two

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111 monomers with aliphatic branch end groups allows the resonances for the diene main chain to be separated from the aliphatic end group resonances. Still, particularly in the case of 9,9TEGOC14, the number of overlapping resonances greatly complicates the interpre tation of this region. The progression from diene monomer through un saturated polymer, to saturated polymer (monitored by 1H and 13C NMR) is shown in Figure 4-7 for 9,9TEGOC14 (4-3c) through TEGOC1421 (4-5c) (arbitrarily chosen as an exam ple). Polymerization to 4-4c results in convergence of the terminal olefin signals in the monomer spectrum to a single peak for internal olefin seen in both the 1H and 13C spectra. Hydrogenation results in the complete elimination of any olefin signal in either the proton or th e carbon spectra. The appearance of only the resonances predicted by the funda mental repeat unit confirm the absence of side reactions and structural irregularities, agai n highlighting the effectiveness of ADMET chemistry in the synthesis of pristine, highly regular polymer stru ctures. Molecular weight data (GPC in THF vs. polystyrene standards) are displayed in Table 4-1. Thermal Analysis The DSC data for the new polym ers are pres ented in Table 4-2. The polymers exhibit remarkably different thermal behavior, a clear indication that cha nging the graft end group moiety has significant effects on the morphology of these systems. The difference in behavior between the saturated and unsaturated polymers is also significant, emphasizing the role of the PE backbone on the crystalliza tion in these materials. The DSC profiles for TEGOPy21 and TEGOPy21u are shown in Figure 4-8. The heating and cooling curves show that th e saturation of the backbone allows for crystallization to occur, while the unsaturated polymer remains completely amorphous. This is clear evidence that the pendant defect is not involved in the crystalliz ation and therefore must be excluded from the crystal. The Tg of the saturated polymer is also slightly increased compared to the unsaturated

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112 analogue, an indication that segmented motion of the grafts is restricted by the crystallinity. The completely amorphous behavior of TEGOPy21u is an interesting resu lt, considering that previous reported unsaturat ed ADMET polymers with the same distribution of pendant functionality are semi crystalline.9-11 The lack of crystallinity in TEGOPy21u, as well as the significantly depressed melting poi nt for the saturated analogue compared to our previous ADMET amphiphilic copolymers15 is a result of pyrene aggregation impeding segmental motion as well as backbone crystallization. This is c onfirmed by pyrene excimer formation seen in the fluorescence spectra for both the unsaturated and saturated polymers (Figure 4-9). The DSC curves for TEGOHex21 and TEGOHex21u are shown in Figure 4-10. The difference in behavior between th e saturated and unsaturated polymer s is especially interesting in this pair. The unsaturated polymer is semicrysta lline with a melting endotherm at -13 C. There is significant amorphous conten t to this material as well, indicated by the distinct Tg at -76 C. The heating and cooling profiles are typical for unsaturated ADMET polymers. The thermal behavior of the saturated analogue is comple tely different, however. A single, bimodal crystallization at -4C is witnessed on cooling. Upon heating a small exotherm is barely observed at -91 C, followed by a bimodal melting endother m with peaks at -48 C and -37 C. A second bimodal melting endotherm occurs w ith peaks at 4 C and 11 C. The complex behavior of TEGOHex21 was furt her investigated by MDSC, which provides increased sensitivity compared to traditional DSC and allows for resolution of overlapping transitions.51, 60-62 The MDSC heating traces are shown in Figure 4-11. In the nonreversing and total heat flow signals the cold crystallization even t, barely perceptible in Figure 4-10, is clearly visible. This is followed by the first bimodal melting endotherm, which is observed in all three signals. In the nonreversing signal th is transition is first exotherm ic, then endothermic, indicating

PAGE 113

113 that the bimodal melt is actually the result of a melting and concurrent crystallization mechanism.60 The same is true for the higher temper ature bimodal endotherm; clear exothermic activity in both the total and nonreversing signals indicates melting and simultaneous crystallization. Because the melti ng enthalpy of this higher temper ature peak (21 J/g) matches the enthalpy of crystallization (21 J/g), and also because its metling temperature and enthalpy (4C and 27 J/g) are in good agreement with those of TEGOPy21 (9C and 24 J/g), it can be concluded that this behavior is a result of crystallization of the backbone excluding the pendant branch. The backbone crystallizes during cooling. Then during subsequent heating, the excluded branches gain sufficient mobility to self crys tallize, noted by the exotherm at -100C. The pendant crystals then melt at about -50C, fo llowed by the melting of the backbone crystals. The thermal behavior of TEGOC1421u and TEGOC1421 (Figure 4-12) diffe rs significantly from the previous two examples. Both polymers exhibit extremely sharp melting transitions at temperatures much higher than the other polymers in this family. This deviates from the well known trend for ADMET polymers, which show a decrease in Tm and Hm as the defect size increases. For TEGOC1421u and TEGOC1421, the increase in pendant group length results in marked increases in both melting te mperature and enthalpy. Further, no Tg is observed in either the saturated or unsaturated analogues, indica ting greatly reduced amorphous content for these polymers. Thus, the long alkyl chains must also be crystallizing. Since there is only one melting peak the C14 chain must be long enough to extend b ack into the crystallizing PE backbone, forming a single crystallized region. Conclusions The synthesis of polyethylene with precise placem ent of amphiphilic grafts has been achieved. These polymers feature PEG grafts attach ed to the polyolefin b ackbone with different hydrophobic groups affixed to the end of the PEG chains. These structural differences induce

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114 significant changes in the therma l behavior of the corresponding materials. When the graft end group is a pyrene moiety, the polyolefin backbone crystallizes excluding the pendant branch. When the end group is changed to an n-hexyl chain, the branches and the backbone crystallize separately, forming two different crystalline re gions. Extending this end group from an n-hexyl to an n-tetradecyl chain allows the branches and bac kbone to crystallize toge ther, resulting in the inclusion of the branch within the PE crystal. This material breaks the well known trend for ADMET polymers, which show a decrease in Tm and Hm as the defect size increases. Most importantly we have demonstrated that a penda nt group can be intentio nally excluded from the crystallized polyethylene backbone and induced to self interact. Th is displays the promise such architectures could have in advanced applicatio ns such as membrane technologies or polymer electrolytes.

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115 Figure 4-1: Synthesis of polyethylene with pr ecisely placed amphiphilic branches. i: NaH, tetra(ethylene glycol)dip-tosylate, DMF; ii: NaH, ROH, DMF; iii: Grubbs 1st generation catalyst, 45 C, vacuum; iv: TSH, TPA, o-xylene, 140 C.

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116 Figure 4-2: 1H and 13C NMR spectra of 9,9TEGOTs (4-2).

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117 Figure 4-3: 1H and 13C NMR spectra of 9,9TEGOPy (4-3a).

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118 Figure 4-4: 1H and 13C NMR spectra of 9,9TEGOHex (4-3b).

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119 Figure 4-5: 1H and 13C NMR spectra of 9,9TEGOC14 (4-3c).

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120 Figure 4-6: Expansion of the aliphatic regions of the 13C spectra of 9,9TEGOPy, 9,9TEGOHex, and 9,9TEGOC14 (3a-c).

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121 Figure 4-7: Progression from m onomer 4-3c to saturated polymer 4-5c monitored by NMR.

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122 Figure 4-8: DSC heating and cooling traces for TEGOPy21u (4-4a) an d TEGOPy21 (4-5a). Figure 4-9: Absorption and fluorescence spectra for TEGOPy21 A) and TEGOPy21u B)

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123 Figure 4-10: DSC heating and cooling traces for TEGOHex21u (4-4b) and TEGOHex21 (4-5b). Figure 4-11: MDSC heating traces for TEGOHex21 (4-5b).

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124 Figure 4-12: DSC heating a nd cooling traces for TEGOC1421u (4-4c) and TEGOC1421 (4-5c).

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125 Table 4-1: Molecular weight data for polymers described in chapter 4. Polymer Mn a (kg/mol) Mw a (kg/mol) PDIb TEGOPy21u (4a) 42.2 80.3 1.9 TEGOPy21 (5a) 31.2 60.4 1.93 TEGOHex21u (4b) 42.8 84.8 1.98 TEGOHex21 (5b) 44.4 79.2 1.78 TEGOC1421u (4c) 36.2 61.9 1.71 TEGOC1421 (5c) 37.3 65.8 1.76 a GPC vs. polystyrene standards; b Mw/Mn Table 4-2: DSC data for polymers described in chapter 4. Polymer Tg (C) Cp (J/gC) Tm (C) Hm (J/g) Tc (C) Hc (J/g) TEGOPy21u -36 0.76 n/a n/a n/a n/a TEGOPy21 -21 0.36 9 24 -12 25 TEGOHex21u -76 0.49 -13 21 -54 21 TEGOHex21 n/a n/a -37, 4 8, 27 -4 28 TEGOC1421u n/a n/a -3 50 -7 51 TEGOC1421 n/a n/a 23 71 17 72

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126 CHAPTER 5 SYNTHESIS OF DEUTERIUM LA BELED ADMET AMPHIPHILES Introduction This dissertation exp lores the effects that altering various paramete rs have on the overall response in a family of material s with related structures. Chapter 2 outlines the basics of this study where altering the distributi on of the hydrophilic branch as well as the identity of the branch end group could affect the ability of the polymer backbone to crystallize. This is further explored in chapter 3 by examining the effect the length of the graft and the manner of its connection to the backbone has on thermal behavi or while keeping the graft end group constant. Chapter 3 also showed that the saturation of th e internal olefin influenced thermal behavior: when the site of unstauration remains the polymers ability of to crystalliz e is greatly hindered or suppressed completely. By consid ering these data we are able to constructe a model for the manner in which the chains fold to allow the crys tallization of the backbon e and the exclusion of the pendant branch. This chapter briefly describes the synthesis of deuterium labeled polymers based on TEGOMe21 (structure 3-8b, pr esented in chapter 3). Solid state 2H NMR has been utilized in the past to gain informati on on polymer molecular motions and dynamics.73-77 Since TEGOMe21 presents both a well defined glass transition and melting endotherm it is an excellent candidate for deuterium la beling and subsequent solid state 2H NMR motion studies on the crystalline and amorphous regions of the polymer. Three labeled TEGOMe21analogues are presented in this chapter. Th e backbone (midway between de fects), the poin t of branch connection, and the branch end grou p were chosen as labeling points since the previous chapters have proven these locations are cr itical in the thermal behavior of these materials (Figure 5-1). Only the synthesis of these polymers is discu ssed here, the solid state NMR experiments are beyond the scope of this dissertation.

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127 Experimental Section Instrumentation All 1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian Associates Mercury 300 spectrometer. Chemical shifts for 1H and 13C NMR were referenced to residual signals from CDCl3 (1H: = 7.27 ppm and 13C: = 77.23 ppm) with 0.03% v/v TMS as an internal reference. Thin layer chromat ography (TLC) was performed on EMD silica gel coated (250 m thickness) glass plates. Developed TLC plates were stained with iodine adsorbed on silica to produce a visible signature Reaction conversions and relative purity of crude products were monitored by TLC and 1H NMR. Fourier transform infrared (FT-IR) measurements were conducted with a Bruker Vector 22 Infrared Spectrophotometer using polymer films cast from chloroform onto KBr plates. High resolution mass spectrometry analyses were performed on a Bruker APEX II 4.7 T Fourier Tran sform Ion Cyclotron Resonance mass spectrometer (Bruker Daltonics, Billerica, MA) using electrospray ionization (ESI). Elemental analysis was carried out at Atlantic Microlab Inc. (Norcross, GA). Molecular weights and molecu lar weight distributions ( Mw/Mn) were determined by gel permeation chromatography (GPC) using a Waters Associates GPCV2000 liquid chromatography system with an internal differe ntial refractive index detector (DRI) and two Waters Styragel HR-5E columns (10 micron pa rticle diameter, 7.8 mm ID, 300 mm length) at 40 C. The mobile phase was HPLC grade tetrahyd rofuran at a flow rate of 1.0 mL/minute. Retention times were calibrated versus polystyrene standards (P olymer Laboratories; Amherst, MA). Differential scanning calorimetry (DSC) and temperature modulated differential scanning calorimetry (MDSC) were performed on a TA Instruments Q1000 equipped with a liquid

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128 nitrogen cooling accessory a nd calibrated using sapphire and high purity indium metal. All samples were prepared in hermetically sealed aluminum pans (4-7 mg/sample) and were referenced to an empty pan. Samples were run under a purge of helium gas. Scan rates of 10C/min and 3C/min were used for DSC and MDSC, respectivel y. Melting temperatures were evaluated as the peak of the melting transition an d glass transition temperat ures as the mid-point of a step change in heat capacity. Materials. Unless otherwise stated, all reagents were purchased from Aldrich and used without further purification. Grubbs 1st generation catalyst was a gift from Materia, Inc. Oligoethoxyptosylates59 and diene acid 5-449 were prepared according to th e literature. 99TEGOMe (3-4b) and 99TEGOTs (4-2) were synthesized as described in chapters 3 and 4 of this dissertation, respectively. 99CD2OH (5-4) was prepared as described in the PhD dissertation of John Sworen.76 TEGOMe21u (3-6b) was obtained from the polymer ization of 99TEGOMe as described in chapter 3 of this dissertation. Synthesis of 99CD2TEGOMe (5-5). Anhydrous DMF (40 mL) was cannula transferred into an oven dried, 3-neck roundbottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and 2g (5.6 mmol) of 5-4 in 20 mL of anhydrous DMF was added via syringe. When gas evolution (monitored by bubbler) ceased, 2.94g (8.1 mmol) of tetraethylene glycol monomethylether ptoluenesulfonate in 20 mL of anhydrous DMF wa s added via syringe. The reaction was stirred for 17 hours at 0 C and quenched by pouring into 300 mL of water. The resulting mixture was extracted with diethyl ether and the combined organics washed with brine. Concentration afforded a yellow oil which was further purifie d by column chromatography. 25% ethyl acetate

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129 75% hexane eluent afforded .710g (2 3% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.211.52 (br, 33H), 2.01 (q, 4H), 3.35 (s, 3H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 2H NMR (CDCl3): (ppm) 3.30 13C NMR (CDCl3): (ppm) 26.92, 29.06, 29.27, 29.63, 29.73, 29.76, 30.20, 31.45, 33.94,38.22, 59.13, 70.50, 70.64, 70.71, 70.75, 72.07, 114.21, 139.29 ESI/HRMS: [M+H]+ calcd for H+C33H62D2O5, 543.4592; found 543.4933. Anal. (CH) calcd for C33H64O5: C, 73.01; H or D, 12.25. Found C, 72.94; H, 11.83. Synthesis of 99TEGOCD3 (5-2) Anhydrous DMF (40 mL) was cannula transferred into an oven dried, 3-neck roundbottom flask equipped with a magnetic stirrer and gas inlet, and was charged with 2 equivalents of sodium hydride (60% dispersion in mineral oil). The slurry was cooled to 0C and .270g (7.5 mmol) of deuterated methanol was added vi a syringe. When gas evolution (monitored by bubbler) ceased, 1g (1.5 mmol) of 99TEGOTs (4-2) in 20 mL of anhydrous DMF was added via syringe. The reaction was stirred for 17 hours at 0 C and quenched by pouring into 300 mL of water. The resulting mixture was extracted with diethyl ether and the combined organics washed with brine. Concentration afforded a yello w oil which was further purified by column chromatography. 25% ethyl acetate 75% hexane eluent afforded .300g (36% yield) of colorless oil. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.29 (d, 2H), 3.50-3.75 (br, 16H) 4.98 (m, 4H), 5.82 (m, 2H). 2H NMR (CDCl3): (ppm) 3.38 13C NMR (CDCl3): (ppm) 26.92, 29.06, 29.27, 29.63, 29.73, 29.76, 30.20, 31.45, 33.94,38.22, 70.50, 70.64, 70.71, 70.75, 72.07, 74.88, 114.21, 139.29 ESI/HRMS: [M+H]+ calcd for H+C33H64O5, 544.5015; found 544.4998. Anal. (CH) calcd for C33H61D3O5: C, 72.88; H or D, 12.42. Found C, 72.66; H or D, 11.86

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130 General Procedure for ADMET Polymerizations Monom ers were dried under vacuum at 80 C for 48 hours prior to polymerization and subsequently transferred to a 50 mL round-botto m flask equipped with a magnetic stir bar. Grubbs 1st generation catalyst (300:1 monomer:catalyst ratio) wa s added and the flask was stirred under vacuum at 45 C for 4 days. Polyme rizations were quenched with ethyl vinyl ether (5 drops in degassed toluene), pr ecipitated into cold, acidic metha nol to remove catalyst residue, and isolated as an adhesive gum. CD2TEGOMe21u. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 (q, 4H), 3.35 (s, 3H), 3.50-3.75 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 27.03, 29.45, 29.76, 29.81, 29.90, 30.00, 30.32, 31.54, 32.83, 38.30, 59.22, 70.55, 70.71, 70.76, 70.80, 72.12, 130.05 (cis olefin), 130.52 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 63800 ; PDI (Mw/Mn) = 1.66 TEGOCD321u. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 33H), 2.01 ( q, 4H), 3.29 (d, 2H), 3.50-3.75 (br, 16H), 5.35 (m, 2H). 13C NMR (CDCl3): (ppm) 27.03, 29.45, 29.76, 29.81, 29.90, 30.00, 30.32, 31.54, 32.83, 38.30, 70.55, 70.71, 70.76, 70.80, 72.12, 74.96, 130.05 (cis olefin), 130.52 (trans olefin). IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 967, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 88700 ; PDI ( Mw/Mn) = 1.64 General Procedure for the TSH Hydrogenation of Unsaturated Polymers Unsaturated polym ers were dissolved in dry o-xylene. p-toluenesulfonyl hydrazide (TSH) and tripropyl amine (TPA) were added with stirri ng (3 equivalents each). The resulting solution was refluxed for 3-4 hours while monitoring n itrogen evolution with a bubbler. When gas

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131 evolution ceased, the solution was cooled to room temperature, an additional 3 equivalents of TSH and TPA were added, and the solution was re fluxed for another 3 hours. The solutions were then concentrated to one-half of the original volume and precipitated into cold, acidic methanol. The polymers were isolated as elastic, adhesive gums. CD2TEGOMe21 (5-7). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H), 3.35 (s, 3H), 3.50-3.75 (br, 16H). 13C NMR (CDCl3): (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 59.25, 70.61, 70.76, 70.83, 70.86, 72.18, IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 77700 ; PDI ( Mw/Mn) = 1.70 TEGOCD321 (5-3). 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 41H), 3.29 (d, 2H), 3.50-3.75 (br, 16H). 13C NMR (CDCl3): (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 70.61, 70.76, 70.83, 70.86, 72.18, 75.03. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 107500 ; PDI ( Mw/Mn) = 1.66 Parr Bomb Deuteration of TEGOMe21d (5-1). Unsaturated, trityl protected polymer TEGOMe21u was dissolved in toluene and added to a glass lined Parr bomb. Wilkinsons catalyst was added and the bomb charged with 700 psi of D2. The reaction was stirred for 3 days at room temperature. The resulting polymers were purified by precipitation into acidic methanol to remove catalyst residue and isolated as an adhesive gum. 1H NMR (CDCl3): (ppm) 1.21-1.52 (br, 39H), 3.29 (d, 2H), 3.35 (s, 3H), 3.503.75 (br, 16H). 13C NMR (CDCl3): (ppm) 27.08, 29.98, 30.37, 31.36, 38.37, 59.25, 70.61, 70.76, 70.83, 70.86, 72.18, 75.03. IR ( cm-1) 2923, 2853, 1464, 1350, 1115, 886, 721. GPC (THF vs. Polystyrene standards): Mw = 81700 ; PDI ( Mw/Mn) = 1.70

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132 Results and Discussion Synthesis and Structural Analysis Figure 5-2 illustrates the s ynthesis of the deuterium labeled T EGOMe21 analogues. To label the backbone TEGOMe21u (3-6b, prepared as described in chap ter 3) was simply saturated with deuterium gas using the parr bomb hydrogenation procedure found in chapter 2. Labeling the branchs methyl end group a nd the branch connection point we re slightly more complicated. To label the branch end group 99TEGOTs (4-2, prep ared as described in chapter 4) was reacted with deuterated sodium methoxide. To label th e branch connection the appropriately labeled diene alcohol 99CD2OH (5-5) was prepared by the LAD reduction of the diene acid 5-4. This alcohol was then used in a Willia mson etherification to yield 99CD2TEGOMe, the reaction conditions identical to the synthesis of th e corresponding unlabeled monomer described in chapter 3. The structures of the deuterium labeled monomers were confirmed by 1H, 13C, and 2H NMR as well as high resolution mass spectrometry and elemental analysis Figure 5-3 shows the 1H NMR spectra of the deuterium labeled m onomers with the unlabeled 99TEGOMe for comparison. In the spectrum for 99CD2TEGOMe the doublet at =3.29 ppm corresponding to the methylene unit directly off the backbone di sappears confirming deuterium labeling at this location. In the spectrum of 99TEGOCD3 the singlet at =3.35 ppm corresponding to the branch methyl end group is absent, confirming the presence of deuterons at this location. Similarly, differences in the 13C NMR spectra (Figure 5-4) betw een the labeled and unlabeled can be seen. Labeling at the methylene unit and me thyl end group results in the splitting of the corresponding carbon signal, slightly visible in the spectrum for 99CD2TEGOMe ( =75 ppm)

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133 and not visible in the spectrum for 99TEGOCD3 ( =59 ppm). In both cases the disappearance of the obvious singlets confirms deuterium la beling has occurred on these carbons As discussed in the chapter 3 (Figure 3-6), polymerization is confirmed by the disappearance of terminal ol efin signals in both the 1H and 13C NMR spectra. Subsequent saturation is confirmed by the disappearance of the internal olefin signal. Thermal Analysis Since the ultim ate goal of this synthesis is to study the dynamics above and below the glass transition and melting temperatures it is essential to confirm that labeling in this fashion will not affect these polymers thermal response. Figure 5-5 shows the DSC overlay for all three labeled polymers. It is clear look ing at the thermogram that the thermal behavior is identi cal in all cases, showing that labeling in this fashion does not alter the thermal behavior of the polymer. Given the consistency in the thermograms it is clear these materials are appropriate for future use in solid state 2H NMR motion studies. Conclusions The polym er TEGOMe21 was deuterium labeled in three locations that have been proven critical throughout this dissertati on in the crystallization and melti ng behavior of this class of materials. The deuterium labeling of these ADM ET amphiphiles is straight forward and requires only small alterations in synthetic method. Labeli ng in the fashion does not affect the thermal behavior of the final polymer. These materials could be useful in solid state 2H NMR motion studies. Such studies could offer further insight into the way these specific locations on the repeat unit of ADMET polymers affect th e crystallization and melting behavior.

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134 Figure 5-1: Locations chosen for deuterium labeling in TEGOMe21 Figure 5-2: Synthesis of deuterium la beled TEGOMe21 analogues; i: Grubbs 1st generation, 45 C, vacuum; ii: Wilkinsons catalyst; 700 psi D2, toluene; iii: NaH, CD3OD, DMF; iv: TSH, TPA, xylenes, 140 C; v: LAD, THF; vi: NaH, TsO(CH2CH2O)4CH3, DMF

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135 Figure 5-3: 1H NMR of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe shown for comparison

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136 Figure 5-4: 13C spectra of deuterium labeled 99TEGOMe analogues. Unlabeled 99TEGOMe shown for comparison

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137 Figure 5-5: DSC overlay of the de uterium labeled TEGOMe21 analogues.

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138 APPENDIX IMPRESSIONS ON LIFE IN KYOTO Hajimemashite As long as I live I will n e ver forget the shouts of irrashaimassen dozo when entering restaurants or shops, or the chants of arigato gozimasu received when leaving. Although I spent only one month in Japan it has le ft an indelible impression. The entire society is set up for efficiency and convenience. There is intense empha sis on being polite, as well as a strong feeling that the collective is much more important th an the individual. This is not to say that individuality is not openly expre ssed and embraced. It is simply s lightly more subtle than in western cultures. There are wisdoms and courtesi es to Japanese culture that escape our own. People with colds, for example, wear gauze mask s to protect others from infection. The emphasis on politeness can be aggravating to an unfamiliar outsider, and could even be misconstrued as open rudeness. For example, no one w ill tell you no. They instead say: musukashi desu ne (literally its difficult). Chotto musukashi desu (its a little difficult) appears to mean down right impossible. Imagine asking if the train you are on goes to your destination and being told that its a bit difficult, only to find out after continuing to ri de that is does not take you anywhere close to where you want to be. Once you begin to recognize the so cial rules and adopt them in your own behavior the atmosphere is warm and inviting. Japan is not at all free of Western influen ce, however. Kyoto, Osaka and Nagoya have the same designer fashion boutiques as Fifth Avenue in Manhattan. The music shops are lined with rare and vintage American guitars. Camera shops contain high end professional equipment from all over the globe. Appearance, it se ems, is very important. At the same time, stealing in Japan is unheard of. In Kyoto I lost a cellular phone on a bus and it was returned to me within days. The lack of thievery coupled with this emphasis on ma terialism perhaps reveals the most striking trait

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139 of Japanese culture: everything fr om possessions to social status must be earned through hard work, honor, and integrity. Amid the vast differences are innumerable a nd comforting similarities. It took no time at all for me to feel at home despite my sophomoric understanding of the la nguage. In the following report I will briefly describe th e cultural experience I had during my visit. This exchange has changed my outlook entirely. I can not wait to return for an extended visit, and I have recommended the trip to everyone Ive talked to since my re turn. To spend time in another culture is essential to understand how small the wo rld we share really is, how alike we all are, and how much we still have to learn from each other. For a graduate student this is of monumental importance, as many of us become th e educators of future ge nerations. We can not teach understanding and tolerance for all people until we are forced to tolerate and understand, as well as be tolerated and understood. My experience in Kyoto has prom oted precisely this. City life in Kyoto I was imm ediately impressed by the cleanliness of the city, the efficiency of the public transportation, and the ease at which this city of about 1.5 million operates. The subway system consists of only 2 lines, which is in sharp contrast to the complicated ne twork of train lines in Nagoya or Osaka. Busses are by far the easiest m eans of transport. They are always on time, reasonably priced (roughly 2 American dollars fo r most rides), and on city busses a number of stops are announced in English. Several private bus lines link to private and public train lines, making travel to surrounding areas very convenient. Restaurants in Kyoto operate with the same ef ficiency as the public transportation. You are welcomed with tea, your order taken, and your check delivered with the food. There is no pressure to hurry, however the minute you stand up your table is bussed and prepared for the next customer. Tipping is not customary. The co st of food varies widely. Family sit down

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140 restaurants (comparable to Applebees or R uby Tuesdays in the US) are about 30% more expensive, the cost per meal around 12-15 USD. Higher quality re staurants (comparable to our downtown restaurants like Liquid Ginger) are much more expensive, typically 30-50 USD for a meal. At some of the more famous sushi restau rants patrons can expect to pay upwards of $500 per person for the experience! Most restaurants of course feature Japanese food, however Chinese, French, and Italian cuisine ar e all very popular throughout Japan. Japanese fast food is similar in cost to US fast food, depending on the meal item and portion. The food is much lower in fat content compared to US fa st food. Food at grocery stores is again comparable to US prices, with the ex ception of beef, which is extremely expensive in Japan. Some western items are widely availabl e such as breakfast cereal and potato chips; however it is difficult to find all of the ingred ients to cook traditional American meals. Entertainment is Kyoto is slightly lower key than other Japanese cities. There are a few pubs, bars, and night clubs. I didn t frequent these, preferring instead to explore the myriad temples, shrines, and shopping arcades for a true look into a foreign culture with a fascinating history. Perhaps the most intere sting feature was the vast subt erranean malls in Kyoto and Nagoya. In such a small country space is a prem ium, and the Japanese are experts and making the most efficient use of this resource. Graduate School in Kyoto The educational system in Japan is very di fferent from our own system. Research groups are run by a team of three faculty members: one full professor, one associate professor, and one assistant professor. There is always more faculty on staff than at American research universities; Osaka Universitys department of Materials Engineering has 60 full professors alone (180 professors if assistant and associate professors are included!)

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141 Students remain at the same school throughout undergraduate, masters, and PhD studies. They are required to finish masters studies befo re working towards a PhD; most students elect to take an industrial job rather th an continuing for a PhD. Regardle ss of the difference in structure the time to a degree is about the same: Japanese graduate students spend 2 years in the masters course and 3 years in the PhD course. All of th is time is spent on research, there is no teaching requirement. Life as a graduate student in Ja pan is not at all unlike life as an American graduate student in the sciences. Most students work 10 to 12 hours days, most work at least one day on the weekend. Some students arrive early, most however begin work around 10 am. This varies from group to group, just like in the USA. The most st riking difference to our university is the time for weekly group meeting: in Japan research groups meet every other Saturday to discuss research. The purpose is 2 fold, it allows every researcher ample time to discuss recent work and get advice, as well as forcing less diligent students to work at least 2 Saturdays a month! In addition, each researcher is expected to give a literature presentation every semester. There is great emphasis on being productive, and a total of 6 publications, split be tween undergraduate, masters, and PhD courses are expected before a PhD degree will be awarded. The length and style of PhD dissertations is very similar to thos e in the USA, and most are written in English. College Sports at Kyoto University I was fortunate enough to join Kyodai Judo Cl ub for one of their practices and get a glim pse into role of extra curricular activities an d athletics at Japanese co lleges. There is really no equivalent at Japanese universities for NCAA college athletics. All sports are operated as clubs. The members, however, take them just as se riously as our college at hletes (perhaps more so!) The Kyodai Judo team practices 6 days a week for at least 3 hours per session. Every other week there are 2 practice se ssion per day Monday through Frida y. This is true not only for

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142 Japanese sports such as judo, kendo, and karate, but also west ern sports like boxing, fencing, volleyball, basket ball, etc. Music and art clubs operate with the same intensity. I was curious how this affected course work; apparently underg raduate studies are very different in Japan. The most rigorous part is the entrance exam. The cour se work is less intense than in the USA, the idea being that Undergraduate time is supposed to be enjoyed before th e responsibilities of professional life set in. Benefit to the University of Florida The benefits of this excha nge program to both the students involved as w ell as the University of Florida itself far outweigh the co sts involved. Kyoto University is one of the top ranked schools in Asia (second only to the Univers ity of Tokyo), as well as being ranked in the top 25 schools in the world. For students, this program allows a glimpse at a different culture with a fascinating history. For students in science particularly this is an eye opening experience, as the lingua franca for the sciences is English. At the poster sessions I attended a number of the presentations reflected this. Although a majority the lectures were in Japane se, most of the power point slides were in English, so it wasnt difficult to follow their st ories. I even attended a few symposia were the language switched from Japanese to English between speakers (questions and discussions included)! Perhaps most surprising was the fact th at these English lectures were usually given by Chinese or Korean speakers. It is especially im portant for American students to witness this. How many of us could enter into scientific discussions in multiple languages? The University of Florida also benefits by strengthening its bond with a globally recognized institution. Kyoto University has been involved in exchange programs with Stanford, Brown, The University of Pennsylvania, the Univ ersity of Michigan, Oxford, and Cambridge to

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143 name a few. The University of Florida certainly belongs among such company, and I hope that we will continue to build this connecti on with colleagues at Kyoto University. Arigato Gozaimashita I would like to extend m y grat itude to Professors Masuda, Sanda, and Shiotsuki for their hospitality, as well and the Dean s office, the College of Libera l Arts and Sciences, and my advisor Ken Wagener for making this dream a reality. I am a changed person after my experience in Japan and I hope I can incorporate th e lessons of patience, tolerance, respect, and curtsey I learned during my visit in all of my future endeavors.

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144 LIST OF REFERENCES 1. Grubbs, R. H. Tetrahedron 2004, 60, (34), 7117-7140. 2. Calderon, N.; Ofstead, E. A.; Ward, J. P.; Judy, W. A.; Scott, K. W. J. Am. Chem. Soc. 1968, 90, (15), 4133-4140. 3. Calderon, N.; Chen, H. Y.; Scott, K. W. Tetrahedron Letters 1967, 8, (34), 3327-3329. 4. Herrison, J.-L.; Chauvin, Y. Makromol. Chem. 1971, (141), 161. 5. Katz, T. J.; McGinnis, J. J. Am. Chem. Soc. 1975, 97, (6), 1592-1594. 6. Grubbs, R. H., Handbook of Metathesis Wiley-VHC: New York, 2003. 7. Lindmark-Hamberg, M.; Wagener, K. B. Macromolecules 1987, 20, (11), 2949-2951. 8. Wagener, K. B.; Boncella, J. M.; Nel, J. G.; Duttweiler, R. P.; Hillmyer, M. A. Die Makromolekulare Chemie 1990, 191, (2), 365-374. 9. Berda, E. B.; Baughman, T. W.; Wagener, K. B. Journal of Polymer Science Part A: Polymer Chemistry 2006, 44, (17), 4981-4989. 10. Baughman, T. W.; Wagener, K. B. Advances in Polymer Science 2005, 176, (Metathesis Polymerization), 1-42. 11. Lehman, S. E.; Wagener, K. B., ADMET Polymerization. In The Handbook of Metathesis Grubbs, R. H., Ed. Wiley: New York, 2003; Vol. 3. 12. Sworen, J. C.; Wagener, K. B. Macromolecules 2007, 40, (13), 4414-4423. 13. Boz, E.; Nemeth, A. J.; Ghiviriga, I. ; Jeon, K.; Alamo, R. G.; Wagener, K. B. Macromolecules 2007, 40, (18), 6545-6551. 14. Boz, E.; Nemeth, Alexander J.; Alam o, Rufina G.; Wagener, Kenneth B. Advanced Synthesis & Catalysis 2007, 349, (1-2), 137-141. 15. Berda, E. B.; Lande, R. E.; Wagener, K. B. Macromolecules 2007. 16. Boz, E.; Wagener, K. B.; Ghosal, A.; Fu, R.; Alamo, R. G. Macromolecules 2006, 39, (13), 4437-4447. 17. Sworen, J. C.; Smith, J. A.; Berg, J. M.; Wagener, K. B. J. Am. Chem. Soc. 2004, 126, (36), 11238-11246. 18. Watson, M. D.; Wagener, K. B. Macromolecules 2000, 33, (24), 8963-8970. 19. Smith, J. A.; Brzezinska, K. R.; Valenti, D. J.; Wagener, K. B. Macromolecules 2000, 33, (10), 3781-3794.

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149 BIOGRAPHICAL SKETCH Erik Benjam in Berda was born in Scranton, PA on September 12th, 1980. Shortly after, parents Pat and Marybeth Berda re located to the Northwest Suburbs of Philadelphia, where Erik spent the remainder of his youth. He discovered chemistry during sophomore year of high school and became immediately enamored. Erik graduate d from Norristown Area High School in June, 1999. He began studies towards a Bachelor of Science Degree in chemistry at Penn State University (PSU), University Park Campus, in August 1999. During his second year at PSU he joined the research group of Prof. Harry R. Allcock, studying phosphazene based polymers for advanced lithium battery applications. Erik also developed a deep passion for teaching at PSU givi ng guitar lessons. This translated fluidly into science while teaching a section of organi c lab in the spring of his senior year. After graduating from PSU in December 2003 Erik moved to the University of Florida in Gainesville to pursue a PhD degree in Organic Ch emistry under the advisement of Prof. Kenneth B. Wagener. During his tour of duty in Gainesvill e, the state of Florida endured record numbers of hurricanes, wild fires, and fatal alligator att acks. Despite this, the Universitys own Gators managed to capture a record number of NCAA national titles. In September 2007 Erik spent a month at Kyoto University in Kyoto, Japan. He successfully completed the requirements for th e PhD degree in March of 2008. After graduation he moved to Europe with longtime girlfriend Dana Gioia to begin postdoctoral studies with Prof. Bert W. Meijer at the Technical Universi ty of Eindhoven in Eindhoven, The Netherlands.


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