Chemistry of conjugated monomers in acyclic diene metathesis (ADMET) polymerization

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Title:
Chemistry of conjugated monomers in acyclic diene metathesis (ADMET) polymerization
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xiii, 172 leaves : ill. ; 29 cm.
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Tao, Dehui, 1946-
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Thesis:
Thesis (Ph. D.)--University of Florida, 1994.
Bibliography:
Includes bibliographical references (leaves 160-171).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Dehui Tao.

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University of Florida
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CHEMISTRY OF CONJUGATED MONOMERS IN
ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION











By

DEHUI TAO


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

4 QQA























dissertation


is dedicated


parents


their


love


and


support.











ACKNOWLEDGEMENTS


This


research


could


have


been


successfully


completed


without


help


professors


fellow


graduate


students.


cordially


appreciate


their


kind


advice


and


scientific


support.


First


would


thank


members


committee


, Drs.


Kenneth


Wagener


John


Zoltewicz


, Randolph


. Duran


, Jame


Boncella


Hendrik


Monkhorst


their


assistance


advice.


Thanks


given


Drs.


Jasson


Patton


Konzelman


Chri


Bauch


, and


Gamble


catalyst


synthesis.


Sincere


thanks


also


given


Drs.


. Brzezin


and


Arno


Wolf


their


instruction


ADMET


technique.


The


supportive


entific


environment


polymer


floor


always


progress


been


in my


helpfu


overcoming


research


Thanks


difficult


given


and


polymer


making
research


groups of Drs.


. Reynolds,


Duran


and G


Butler


and to the


past


and


present


members


of the


Wagener


group,


including


Drs.


Fabio


uluaga,


Chr


Dennis


mith


Marmo


Kathleen


sson


Novak


Portm


ess,


Chri


Tammy


Matayabas,


David


as wel


Sophia


Cummings,


Dominick


Valenti


Shane


Wolf.


special


thanks


Drs.


John


O'Gara


and


Michae


DiVerdi


their


tireless


help


and


advice


a a a -^ a a.a-. ai:


LI


(~ YYI:LI


,I A,JL


a I






Thanks


given


National


Science


Foundation


(DMR-


8912026)


and


Products


Corporation


their


support


work.


Fina
Wagener I


sincere


thanks


support,


understanding,


advisor
and a


Professor


guidance


Kenneth


throughout


entire


graduate


school


years


University


Florida.











TABLE OF CONTENTS






ACKNOW LEDGEMENTS ............................................. ............. .. .. ................ ........... iii

ABSTRACT.................... ................................................................................... ...........xi

CHAPTERS


NTRO DUCTIO N ............................. ................................................ .............1


The


Synthese


, Properties


Applications


Polyacetylene


Historical


( PA)


Development


Poly(phenylene vinylene)


Olefin


(PPV)............... .2


Metathes


The Metal Carbene Mechanism... .......... .. ........ ........... .... .. ........... .......13


Development


Lewis


Acid-Free


Metathesis


Catalysts


Ring


Opening


Metathesis


Polymeri


action


(ROMP)


Acetylene Metathesis Polymerization


and


.................23


Acyclic

Study


, Diene

on the


Metathesis

Chemistry


(ADMET)


Polymerization......................29


Conjugated


n ADM ET Polymerization..


Monomers
s a.............................. ......... .3 5


EX PER IM ENTA L ....... ................. ..... .......... ....... .. ......................................... 37


Chemistry .....,.,.,,.8








General ADMET Reaction

NMR Solution Reactions...


Tech niqcu es ................ ................... ..............40


.......... ................................ ......... ........ ................4


ADMET Polymerization of 2,4-Hexadiene 2................... ................. ...41

Bulk Polymerization of 2,4-Hexadiene 2. .................. ....................4.. 1


Solution


Polymerization of 2,4-Hexadiene 2.................... .........43


Synthesis


and


Polymerization


2,4,6-Octatriene


Synthesis


Oct-6-ene-3-yne


-2,5-diol


Synthesis of 2,4,6-Octatriene 4 ...................................45


Bulk


Polymerization


2 ,4 ,6-Octatriene 4...... ... ............ .46


Attempted


ADMET


Polymerization


3-Butadiene


a ...... ....


Attempted


Bulk


Polymer


zation


1,3-Butadiene 6.


NMR


Reaction


1,3-Butadiene


Molybdenum catalyst lc.


e....atttets.e..aeaa eeee.*...eeeatetti4


Attempted


Attempted


ADMET


Bulk


Polymerization


Polymer


3,5-Hexatriene


zation


1 ,3,5-Hexatriene


e........ .. ... .. .... .. ........e.t.......48


NMR


Reaction


1.3.5-Hexatriene


and


Molybdenum Catalyst lc....


..... ...... .. .......... .. .. ........ ........49


Synthesis


and


Polymerization


2,10-dodecadiene


9.................49


ynthe


,8-octylenebi


s(triphenylpho


sphonium
.................... ...........g.49


bromide) 8..


4. ................44


III1IIIIIIIIIII11~LI11111111111111111111 ..47


.. .. .. .44


Z. .48







Syntheses of


Poly(acetylene-co-octenamers) .........................51


Attempted


copolymerization


2.4-hexadiene


and 1,9-decadiene 11.


Synthesis
1:1 Ratio 12.


Synthesis


Poly(acetylene-co-octenamer)


Poly(acetylene-co-octenamer)


Ratio 13.


...............................53


Synthesis
1:4 Ratio 14.


Synthesis
2:1 Ratio 15.


Synthesis
4:1 Ratio 16.


Poly(acetylene-co-octenamer)


Poly(acetylene-co-octenamer)
......................................c..c............................................t....5454t1


Poly(acetylene-co-octenamer)
..6Oo~l WIO *O .,OOIOt lmlIIOImo oIII ~ I.oORIWOI.eIIII .Iomo5 5


Attempted


Polymerization


cis. cis-1


,4-Dicyano-


1,3-butadiene 17......


Attempted


Solution


Polymerization


cis,cis-1,4-Dicyano-1 ,3-butadiene


............ e................ ... .56


NMR


Reaction


cis, cis-


1,4-Dicyano-1 ,3-butadiene


Attempted


Polymerization


trans


trans-


1,4-Diphenyl-1 ,3-butadiene 18


e. .......e. *ee.....e. 5t5*e....... ..56


Attempted


Solution


polymerization


trans,trans-1 ,4-dipheny


3-butadiene


NMR


Reaction


trans, trans-


1,4-diphenyl-1 ,3-butadiene 18................... .................. ................ ..57


Synthesis of


Isobutyl-Terminated


Polyoctenamer


................... .............52


17 .........,.,...., ............,..... ...............,., 56


............ ............51


IIIIIIIIIIIIII


1 8..............................57


~n. .57








Attempted


Bulk


Polymerization


2.4-Hexadiene


with 4-Meth y l -pentene.


.................. 58


NMR


Reaction


2,4-Hexadiene


4-Methy


-pentene


with Molybdenum Catalyst ic....


.......59


Metathesis


Coup


Reaction


Functiona


ized


Terminal Olefin


S .....


Attempted

Attempted


Metathesis

Metathesis


Coupling

Coupling


Chloride


Amine


21.............59


22.... .............59


Attempted


Metathe


Coup


3-Butena


Diether Acetal


.6c~


23.......


Attempted


Metathesis


Coupling


5-Hexen


-one


24..........60


Metathesis


Metathesis


Coupling


Coupling


4-Methyl- -pentene


4-Penten-


1 9. ........ 35Sf *43*333.6


-acetate


Metathesis


Coupling


Allyltrimethylsilane


Syntheses of Telechelic Polyacetylen


Synthesis

Synthesis


Hexyl-Terminated

Isobutyl-Terminate


Polyacetylene 32

d Polyacetylene


33 .......... 63


Synthesis


Pheny


Terminated


Polyacetylene


Synthesis


Trimethylsily


Methylene-


Terminated


Polyacetylene 36


S......... .... ..65


Synthesis c
Polyacetylene


Acetate-propy


Terminated


...... ....,,................


27 6


29 ... .62


es..... .. .. ...... ...........63


................... ........59


35 .64








Synthesis of 1 ,3-Dipropenylbenzene 40................................. ...... 67


Synthesis of


Poly(1


phenylene vinylene)


41 .... .. ... .. .......... .68


Synthesis of


Poly(1 ,3 -phenylene vinylene)


42........ ................. 68


Synthesis


and


Polymer


action


8-Octeny


p-propenylbenzene 44...


550ccact t e.......... ...............6


Synthes


Synthesis


Polymerizatio


4- Bromo-1


8-Octeny

n of 8-C


-propenylbenzene 4... .......... ..............69


-p-propenylbenzene


)cteny


-p-propenylber


44 .. ............... ...... 69

nzene 44.............70


Synthese


Poly(phenylenevinylene-co-


octenamers) ....

Synthesis
1:1 Ratio 46.

Synthesis
4:1 Ratio 47.

Synthesis
1:4 Ratio 48.


..................... ....................7


Poly(1


,2-phenylenevinylene-co-octenamer)


.....7


Poly(1


,2-phenylenevinylene-co-octenamer)


*....7


Poly(1


,2-phenylenevinylene-co-octenamer)
.. ..t.e ........tt.........t........... ............... ... .. s. e............73


Synthesis


Poly(octenamer-co-


1,2-phenylenevinylene) 49.


Synthesi


Block


Poly(1


co-octenamer) 50.


,2-phenylenevinylene-
. .. ....e .. a.. m..... ... ......... ... .. ... ... ... ... ...74


Synthesis
1:1 Ratio 51.

Synthesis
4:1 Ratio 52.


Poly(1


Poly(1


,3-phenylenevinylene-co-octenamer)
.a..t... .eee...... .t...... ......... ee.... ..e.....e.. .. e .... ..a......c...e /75

,3-phenylenevinylene-co-octenamer)
........................ ..... ....... ., ...............,....,. .......76







Metathesis


Reaction


Propenylbenzene


and 1-Nonene...


REACTIVITIES OF CONJUGATED DIENES AND


TRIENES


N ADMET POLYMERIZATION


The


Polymerization


Chemistry


nterna


Conjugated Dienes......


.......................................80


Solution


ADMET


Polymerization


versus


Bulk ADMET Polymerization..........


...... .....................................8 5


ADMET


Polymeri


action


nterna


Conjugated Triene,


2,4,6-Octatriene...


investigation


on the


Reactions


Termina


Conjugated


Dienes and Trienes


with a Molybdenum Catalyst.


Copolymerization of
a Nonconjugated Diene


2,4-Hexadiene
......i..ii ... ..t.i. iie i i s..


and
..................................................92


Conclusion


SYNTHESIS OF TELECHELIC POLYACETYLENES
THROUGH ADMET POLYMERIZATION.............. ...


Polymerizab


Functional


Group-


Terminated


1,3-Butadien


es.... ..


Mode


Study


--Synthesis


Teleche


Polymer


through


ADMET


Polymerization


9-Decadiene


and a Monoolefin.........


.....................108


The


Reaction


Between


2.4-Hexadiene


and


Terminal Monoolefins ....


555555 **-tb*Si C *i~i C a... ii... 55


investigation n


.21I L* Li


"Nenative


Neinhborina


Ground


Effect"


.................... .............,.., ....87


s....................................... ....98


.... .90


..................1 00






Synthesis
ADMET F


Telechelic


'olymerization


Polyacetylenes
f 2,4-Hexadiene


Through
and


Internal Monoolefins.............


.......a..............................1 20


C conclusions .............................. ................................................ .................23


ADMET POLYMERIZATION AND COPOLYMERIZATION


OF DIPROPENYLBENZENES...


ADMET

ADMET


Polymerization

Polymerization


1 ,3-Dipropenylbenzene .......................125


Dipropenylbenzene .....................1 31


Copolymerization
with 1,9-Decadiene.


and


,3-Dipropenylben


zene


..............137


Discussion


Reactivities


Between


Conjugated


Dienes and Nonconjugated Dienes.......


SSS*CSCS S S SS C S *S* S.C.. ..... S at '16


Conclusions ................... .................................... ............................... 153


SUMMARY OF DISSERTATION. ....................... .... ................................1 54


REFERiENCIES ................... ................... ................... ........e5..e......t..a............... ...... i.60


BIOGRAPHICAL SKETCH ............. ..** St.........~ U.S......... ...................172











Abstract of Dissertation


Presented to


the Graduate School


of the


University


Florida


Partial


Fulfillment


of the


Requirements for the Degree of Doctor of Philosophy


CHEMISTRY OF CONJUGATED MONOMERS IN
ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION

By


Dehu


April


Tao


1994


Chairman: Dr. Kenneth B. Wagener


Major


Department


Chemistry


A study of the chemistry of conjugated monomers, such as 2,4-


hexadiene


and


dipropenylbenzene,


acyclic


diene


metathesis


(ADMET)


polymerization


is presented.


Conjugated polymers and their


copolymers


have


been


synthesized through


ADMET


polymerization of


corresponding


monomers


using


well-defined


alkylidene


complexes


type


M(CHR)(N


,6-C6H3


Pr2)[OCH3(CF3)


(M=W


or Mo;


=CMe3 or CMe2Ph) as catalysts


Methyl-terminated


polyacetylene


oligomers


were


successfully


synthesized


through


ADMET


polymerization


internal


conjugated


dienes


2,4-hexadiene


and


4,6-octatriene.


Solution


polymerization


2.4-hexadiene


produced


longer


polyacetylene






productive


catalyst


was


ADMET


decomposed


polymerization,


monomers.


since


Block


. molybdenum

poly(acetylene-


co-octenamers)
hexadiene and


were


obtained


through


copolymerization


2,4-


2.10-dodecadiene.


Telechelic


polymerization
7-tetradecene,


polyacetylenes
2,4-hexadiene


propenyl


were


with


benzene,


synthesized


internal


through


monoolefins,


ADMET
such as


1,4-bis(trimethylsilyl)-2-butene,


and


The


4-octene-1,8-diyl


ADMET


acetate


polymerization


, but


with


functional


terminal


monoolefins.


group-terminated


1.3-


butadienes


was


successful,


either


because


steric


hindrance


prohibiting


ADMET


reaction


because


non-productive


reaction


stopped


ADMET


polymerization


Poly(1,2-phenylene


vinylene)


and


poly(1,3-phenylene


vinylene)


ollgomers


were


synthesized


through


ADMET


polymerization


dipropenylbenzene
copolymerization


and


1,3-dipropenylbenzene,


1,2-dipropenylben


respectively


zene


and


. The


1,3-


dipropenylbenzene


random


statistics


with


1,9-decadiene


structural


produced


distributions


copolymers


based


having
initial


monomer


octenamer)


feed


was


ratios.


obtained


Block


through


poly(1


-phenylenevinylene-co-


addition


1,9-decadiene


poly(1,2-phenylene
to polyoctenamer,


vinylene);


addition


1,2-dipropenylbenzene


however, produced a random copolymer.











CHAPTER 1
INTRODUCTION


Polymer science and technology have had a profound


influence


material


quality
, from


20th


plastics


and


synthetic


century


fibers


Indeed


synthetic


polymeric
rubbers,


be seen


everywhere


in daily


They


are also widely used


industry


engineering


material


replace


traditional,


naturally


occurring


materials,


such


metals


and


cellulosic


compounds,


because


range


their


physical


relative


and


ease


chemical


manufacture


properties,


and


and


fabrication


raw


wide


material


cost.


The pioneering work of Staudinger,


Mark,


Carothers,


and others


1920s


and


1930s1-8


foundation


"plastic


age"


establishing


molecular


principles


governing


formation


and


properties of polymers.


These early workers


paved the way for


variety


synthetic


polymers


that


have


characterized


last 60


years.


This


dissertation


deals


with


new


polymerization


chemistry, known
polymerization. The


polymerization


acyclic


research


conjugated


diene


represents an


monomers


metathesis
effort to ext


which


(ADMET)


:end ADMET


olefins






investigated,
synthesized


and


basic


conjugated


physical


polymers


and


chemical


polyacetylene,


properties


poly(phenylene


vinylene),


and their derivatives are examined.


iteratu re


review


presented


first


order


obtain


better


understanding


these


conjugated


polymers


and


ADMET


polymerization


related


metathesis


chemistry


and


metal


catalysts.


The Syntheses.


Properties and Applications of


Polyacetylene (PA)


and Polv(phenylene vinylene) (PPV)


Conjugated


polymers


(Figure


1.1)


currently


attracting


considerable


interest


because


their


conducting


and


nonlinear


optical
including


properties.


high


They


have


wide


batteries


variety


applications


electronic devices,


and


nonlinear


optical


devices


, and


even


potential


replacements


metal


wires.


sw~r


Polyacetylene


Polyphenylene


ann-~


=- a


poly(phenylne


vinylene)


Polythiophene


power rechargeable






From


represent


materials


attempt


science


combine


point
e the


view,


electrical


conducting
behavior


polymers


metals


with


mechanic


properties


plastics.


The


versatility,


environmental


stability,


ease


fabrication


and


light


weight


conducting


polymers


make


them


fascinating


materials


electronic


devices.


Since


standing,


Ivery


Shirakawa


and


kada9


polyacetylene


1974


first


and


synthe
found


zed


free-


that


high


conductivity


been


devoted


extensive


this


theoretical


polymer,


and


which


experimental


kept


research


polyacetylene


research as one of the


most active areas of study.


The conductivity


polyacetylene


manipulated


over


enormous


range


values,


from


insulator


(10-1


mho/cm)


good


conductor


(103


mho/cm)


by doping.


Conjugated


polymers


inherently


possess


very


high


nonlinear


optical


(NLO)


photoexcitation


found


decay


response.


across


very


the gap
rapidly (


10-18


produces


trans


electron


sec)


polyacetylene,
hole pairs that are


pairs


separated,


positively


note


that


and


this


negatively


process


charged


results


solitons.19-23


efficient


charge


important to
separation


mechanism,


feature


essential


providing


large


optical


nonlineariti


24-26


The


large


values


of third


order


susceptibility


(c(3)(w)) i
historically


short polyacetylene oligomers (also


been


important


because


they


called


polyenes)


simplest


conjugate


system.


Drury28


reported


samp


oriented


fully


dense


10-3




4

Polyacetylene can also be used as a gas separation membrane,


such


membrane


disubstituted


polyacetylene,


poly[1-


(trimethylsilyl)-1 -propyne]


[P(TMSP)].


The


P(TMSP)


membrane


prepared


solvent


casting


shows


extremely


high


permeability


oxygen


and


nitrogen


gases.29-31


example,


permeability


coefficient for oxygen through the glassy P(TMSP)


membrane at room


temperature


polydimethylsiloxane


about


times


membrane


which


high
been


that


known


through


show the


highest value among nonporous


polymer membranes.32


Polyene


chain


(short


length


polyacetylene)


also


important


components


natural


products,33-36


such


as a


wide


variety


natural


carotenoids


found


fruits,


vegetables,


and


poultry


The


from


first


acetylene


linear


Natta


conjugated


Mazzanti


polyacetylene


and


was


Corradini3


synthesized


1958 using a


Ti(OBu)4/AIEt3


catalyst at a


concentration


a few


millimolars


monomer.


Later,


They


a number


obtained


of polyacetylenes


insoluble


were


, infusible


synthesized


, gray
using


powder.
transition


metal


catalysts


with


varying


degrees


efficiency.38-40


With the


same


and


Ti(OBu)4-AIEt3


reaction


catalyst


temperatures


, Hatano


varying
et al.41


concentration,


were


able


solvent,


prepare


polyacetylene


with


varying


degrees


crystallinity,


and


less


than


of the


reaction


benzene.4


It appears


that this catalyst


produces


higher


yields


near


polyacetylene


than


other


systems


investigated.






acetylene


metathesis


block


copolymers


polymerization


anionic,


methods


been


Ziegler-Natta,
reported.43-47


and


example


formation


poly(acetylene-co-styrene)


through


Ziegler-Natta


polymerization


ustrated


Figure


where


double-labeling


experiment,


utilizing


14C


and tritium


, was employed


show


that


copolymer


polyacetylene


homopolymer


was


forming.44
growing p<


Graft


copolymers


olyacetylene


were


chain


synthesized


solution


was


where
grafted


either
onto


solub


carrier


polymer


chain


was


polymerized


carrier polymer as a side chain.


nBu


LL Ti(OBu)4
Ph


n ,u/Ti(OBu)3
nBu 7n n


LiOBu


m+1 C2H2


Figure


Copolymerization


of acetylene


and


styrene


using


Ti(OBu)4 as catalyst.


Synth


eses


polyacetylenes


through


ring


opening


metathesis


polymerization


and


acetylene


metath


esis


polymerization


discussed


later


chapter


Polyacetylene


usually


gray


black


semicrystalline


powder


which


melting.48


insoluble


Polyacetylene


solvent


very


and


reactive


decomposes
macromolecule


before


being






spectra
spinning


have


been


several


obtained


with cross


groups,49-51


who


polarization


have


and


determined


magic angle


that


trans-polyacetylene


chemical


shift


136


139


ppm


downfield


from


tetramethylsilane


(TMS)


while


cis-polyacetylene


is 126 to


129 ppm.


Poly(phenylene


vinylene)


(PPV)


represents


combination


chemical


structures


between


polyphenylene


(PPP)


and


polyacetylene


(PA)


and


favorable


electronic


properties


these


prototype
vinylene)


polymers


has


also


(Figure


1.3).


served


long


time


model


poly(phenylene


analogous


polyphenylenes


and


polyacetylenes.


Poly(phenylene


vinylene)


photoconductor


with


band


gap


and


high


conductivity


can


reached


appropriate


chemical


electrochemical


treatment.


Polymer


Structure


Eg (ev)


IP (ev)


Polyacetylene


Poly(1,4-phenylene)


Poly(phenylene


vinylene)


CH =CH-n


Figure


The


structures


polyacetylene,


poly(1,4-phenylene),


and poly(phenylene vinylene), and their band gap (Eg)


and


ionization


potential(IP).55


eV,55






oligomers


were


formed


these


reactions.


Wessling


and


immerman57


and


Kanbe


and


Okawara58


1968,


and


later


Capistran


using


et al.,59


a soluble


Gagnon


precursor


et al.,60


Murase


polymer for the


et a..61,6


preparation


reported


PPV.


The


method


(Figure


1.4)


involves


preparation


of a


bis-sulfonium


salt for


parent


PPV


followed


elimination-polyme


rization


reaction


produce an


aqueous


solution


of precursor polymer


This


polymer


can be processed


into films,


foams


and fibers.57-61


Heating a cast


precursor polymer


at 200


more


than


2 h


results


yellow


free-standing


PPV


CICH


H2CI + (CH3)2S'-(CH3)2S+-CH2


CH2-(CH3)2


2CI


+NaOH


- (CH3)2
C)-H-CH2


CHCH)-
/n


+ (CH3)2S + HCI


PPV


Figure


A scheme for the preparation of PPV by the precursor


method.


Unsubstituted


PPV


appears


yellow


whereas


cyano


methoxy substitution cause a color shift to orange and deep red.


other


yellow.


hand,


When


pheny


PPV


substitution


was


chang


examined


absorption


differential


ight


scanning


calorimetry


(DSC)


,no g


or melt transition


was observed between


-196


and


500


Decomposition


begins


about


550


nitrnnrn


atmncnh rs 63


Q-1+ n r_


mith


,t a' 64


ronnrtPd


that the


t~~ ~ ~ I l Ewin t S IIIr tU s rA. *U %SJJ Lt*..A~ U* 5L *






chloride]


shows


slightly


longer


UV/vis


wavelength


absorption


maximum


, because


polymer


fewer


hybridized


carbon


atoms


and


therefore


onger


conjugation


engths


polymer


Historica


Development


Olefin


Metathesis


Chemistry


The


olefin


metath


esis


reaction


considered


very


success


organic


reaction


with


many


app


cations


both


molecular


weight


range


and


polymer


field.


one


would


have


predicted


1950s


or early


1960


that


reaction


which


double


even


bond


remotely


is apparently


cleaved


possible.


only


and


reassembled


it possible,


also


was


in some


cases


proceed


equilibrium


within


seconds.


The


word


metathesiss"


original


from


Greek


meta


meaning
chemistry


"change"


and


refers


tithemi


meaning


interchange


"place.


Metathe


parts


stances


form


new


stances


such


metath


esis


reaction


between


salts


acid


and


bases


organic


chemistry.


The


term


olefinn
carbon


metath e
atoms


" is


commonly


between


pair


used


double


express
bonds


nterchange


resulting


formation


new


olefins


(Figure


I


R2


R4


R


R3~RI








Olefin


metathesis


reactions


classified


three


basic


categories:
productive


(Figure


and


1.7);65


te exchange
degenerate


and


reaction


(Figure 1
polymer


which


types


degradation


zation


reactions


known,


reactions


both


ring


opening


condensation


types


(Figure


CH3CH=0CH2


CH3CH=CH2


CH3CH


CH3CH


II
CH2


Productive


metathes


CH3CH=CH2


+CH2=CHCH3
CH2=CHCH3


CH3CH
II
CH2


CH2


CHCH3


Degenerate


metathesis.


Figure


Olefin


exchange


metathesis


reaction.


,-%%


Figure


Degradation


metathesis


reaction.




10


(-CH2CH2CH2-CH=CH


Ring opening metathesis polymerization


4R% F


(ROMP).


SR-CHCH -


Acyclic diene


metathesis


(ADMET)


polymerization.


Figure


Metathesis


polymerizations.


The


expression


olefinn


metathesis"


was


coined


Calderon


1967,66 and until that time


opening


metathesis


the chemistry


polymerization


of exchange
1 developed


reactions and


independently.


The


first


metathesis


work


was


ring


opening


metathesis


polymerization


cyclopentene


and


norbornene


MoO3/A1203 and


activated


with


LiAIH4


1957.67


This


was


followed


1960


open


opening


publication


metathesis


from


same


polymerization


laboratories


(ROMP)


describing
norbornene


ring


TiCI4/


LiAIR4.68


Soon


afterwards


it was discovered


Natta's group that


cyclobutene69


and


cyclopentene70


would


undergo


ROMP


presence


TiCI4/Et3AI


, MoCI3/Et3AI, or WCI6/Et3AI, even at a low


temperature(-50


"C),


and


that the


fraction


double


bonds


was


dependent on the conditions.


RuCI3 was also found to be effective in


conducting


ROMP


cyclobutene


and


derivatives


water


alcohol


meantime


, following


first


patent7


1960


which


closed


disproportionation
-7 -


propene


--


-


--







Mo(CO)6/AL203


operating


The


metathesis of propene


(Figure


and


1.9)


was


beginning


subsequently


1966


developed


process


was


industrial


operated


process,


years


Shawinigan Chemical Co.


2 CH3CH=CH2


n Montreal.


CH3C3CH=CHCH3 + C2H4


Figure


Metathesis


reaction


of propene.


1967


Calderon


et al.66,74


made


important


discovery


that


catalyst


system


WCI6/EtAIC


/EtOH


(1/4/1)


would


cause


only


very


rapid


ROMP


cyclopentene


also


disproportionation


2-pentene


room


temperature.


This


discovery


were


provided


examp


bridge


one


and


that


same


realization


chemical


that


reaction


these
n.74


Furthermore,


reaction


between


2-butene


and


butene-d8


only


2-butene-d4


(Figure


1.10),


demonstrating


that


double


bonds


themselves


were


completely


broken


chemical


reaction.75,76


CH3CH=CHCH3
+
CD3CD=CDCD3


CH3CH
II
CD3CD


CHCH3
II
CDCD3


Figure


1.10


. Metathesis


disproportionation


reaction.


The cross


first


reported


metathesis
a patent7


between


1966


a cyclic and


using


acyclic


olefin


was


moblydenum-based






CH2


CH2


CH=CH2
CH=CH2


Figure


1.11.


Cross metathesis


reaction.


Olefin


require


metathesis


catalyst


reactions do
system.65,78


occur spontaneously.


The


early


metathesis


They


catalyst


systems


mixture,


closely
which a


resemble


later


Ziegler-Natta


referred


polymerization


"classical


catalysts."


catalyst


Those


catalysts are


based


upon


transition


metals:


and


(group


IVA)


Nb and Ta (group


Mo and W (group


VIA); Re (group VIIA);


and


(group


VIllA).


The


most


effective


catalysts


have


either Mo


, W, or Re as the active metal center.


The


"classical"


olefin


metathesis


catalysts


cons


heterogeneou


homogeneou


trans


ition


metal


compound,


frequently


conjunction


with


Lewis


acid


co-catalyst


and


sometimes


third


promoter.


79,80


Many


more


complex


multi-


component formulations


have also been


investigated with


the goal


controlling
book.65


selectivity
Examples


which


been


homogeneous


reviewed


catalyst


detail


Ivin's


formulations


[Mo(NO


2(L)2C


2]-[R3AI


2C1l381-84


(L=PPh3;


=Me


, Et),


WC16-


EtOH


77.85


WOCI4-


nMe4,86


MeReO3-AIC13,87


and


[Re(CO)5CI]-


EtAIC


Many of these and closely related species have also been


supported


polymer resins.89-91




13

The Metal Carbene Mechanism


Once it was clear that the double bonds themselves were being


broken


olefin


metathesis


reaction,


different


mechanisms


were


proposed


chemists


explain


metathesis


reaction


processes.


Natta


a!i.92


originally


proposed


mechanism


involving


cleavage of the alpha carbon-carbon a bonds,


which was not accepted


later


chemists


. In


1967


, Bradshaw


al. 93


suggested


"quasicyclobutane"


intermediate


attempt


explain


disproportionation


metathesis


reaction


propene


(Figure


1.12)


report


which


they


claimed that there


was


enough


information


to propose an actual mechanism.


00=0


---C


CC=C


IcI---
CC -C


Figure


Bradshaw's


quasicyclobutane


intermediate


proposed


for the


metathesis


disproportionation


propene.


Later


Calderon


and


coworkers.74-75


offered


additional


support


and


detailed


investigation


for this


mechanism


and


proposed


that


transition


metal


provided


orbita


that


overlapped


those


associated with


carbon-carbon


double


bonds


such


a way


facilitate


metathesis


weakly


held


cyclobutane-type


complex.


mechanism"


This


(Figure


mechanism


1.13)


which


, explained the


became


known


metathesis


"pairwise


reaction


so well


LL .J


- .'- .


-~I


J. I A


rn rll *i rt n r Tn fi .- n nfl n nn ns n r r U rnlnn rnrn r .f lU


+a;ma


Tk;r


mn*nk-n n m


r


,,, I,.,,,








[Mt]


C ---c
[Mt]
C ---C


C=C
[Mt]
C-C


Figure


1.13


Calderon


pairwise


mechanism


olefin


metathesis.


Since


1975,


evidence


in favor of the metal carbene mechanism


become


compelling


that


pairwise


mechanism


been


finally


suggests


abandoned.


that


The


non-pairwise


reaction


occurs


metal


through


carbene


mechanism


reversible


[2+2]


cycloaddition


a carbon-carbon double bond


a metal carbene


form


metallacyclobutane


intermediate


which


then


cleave


produce a new olefin


(Figure


1.14).


A metal carbene


is regenerated


at every stage.


o c

M


+
[M-I C


Figure


1.14


The


metal carbene mechanism of olefin


metathesis


reaction.


The


carbene


mechanism


was


first


proposed


1970


Herisson


and


Chauvin94


bas


cross-metathesis


experiments


using


cyclopentene


and


unsymmetric


olefin,


pentene


(Figure


1.15).


The


statistical


product


mixture


obtained


this


reaction


difficult


explain


pairwise


reaction


mechanism


, since it would lead one to expect that the cross reaction


SI S S C -~ I


*


I i., I,


r


*


* *







WOCl4/Bu4Sn


and


WOCI4/Et2AICI


chlorobenzene


catalysts,


Herisson


and


Chauvin


found


three


products


(C9,


C10


, and C11


Figure


1.15


statistical


ratio


even


initial


products,


and


it was


observation


that


them


propose


metal carbene chain


cyclooctene,


mechanism.


1,5-cyclooctadiene,


Similar

and


results were obtained with


1,5,9-cyclododecatriene


place of cyclopentene.


Et


[Mt]
r,,..i.


Mt
---
[Mt]:
-- -1
Et


Sr,


=-Et


Cross-metathesis


reaction


through


pai rwise


mechanism.


.=-Mt
,=-Mt

,=-Mt
,=-Et


=-Et


Cross-metathesis


reaction


through


metal


carbene


mechanism.


Figure


1.15.


Cross-metathesis


pentene


through


reaction
different


cyclopenetene


and


mechanism.


The
v rnl inr4


formation


4 A- Ynet


three


I I a a


series


A A a a a a n


products


-A a AC; Aa


*181331C` I Elli 8IUi ***I flU ta Su U I1 I' Y~ r


could


(gin, ira


.L
-r


=-Et


r






Q2=propylidene


(EtCH=)],


cyclopentene


represented


metal


catalyst represented as [Mt]


and Q1MnQ1


, Q1MnQ2 (equal to Q2MnQ1),


and


Q2MnQ2


are the


three series of products.


more detailed


study


of this


type


reaction,


Katz


and


McGinnis95 found


that


case


cyclooctene/2-hexene,


initial


ratio


three


products,


as determined


extrapolation


zero


time,


was


1:3.2:1


C14:C16). A


more clear-cut experiment is to


react cyclooctene


with


mixture


2-butene


and


4-octene,


"double


cross-


metathesis"


reaction.


Using


MoCI2(NO)2(PPh3)


2/Me3AI3Cl3


chlorobenzene


as catalyst,


Katz


and


McGinnis


found


that


initial


product


ratio


(C14/C12)(C14/C16)


was


4.05+0.05


reactants


and


4.110.09


trans


metal


reactants,
carbene n


compared


mechanism,


with
zero


predicted


values

simple


pairwise


mechanism


, and


about


pairw


, sticky-olefin


mechanism.


experiment


shows


clearly


that


types


pairwise


mechanisms


must


rejected.


[Mt]=Q


[Mt]=MnQ1


+ n M- -


[Mt]=MQ1


[Mt]=Q2
+QQt]=Q
\ Mt]=Q1


+Q1MnQ1


+ Q2MnQ1


[Mt]=Q2


+n M--


[Mt]=MnQ2


[Mt]=MnQ


+ Q1Q2


[Mt]=Q1 -


[Mt]=Q2


2 (4)


SQ2 MnQ2


+Q1 MnQ2








Ring


opening


metathesis


polymerization


offers


more


evidence


metal


carbene


mechanism.


The


products


ROMP


reaction


having
weight


generally


molecular


fraction


consist


weight


consisting


high


molecular weight fraction


excess


series


and


cyclic


, often


molecular


oligomers.


Such


behavior


cyclooctene,


been


observed,


1,5-cyclooctadiene,


example,


cyclododecene


with


and


cyclopentene,
norbornene.65


According


simple


pairwise


mechanism


one


would


expect that


molecular


weight


product


would


gradually


increase


cyc


oligomers


increasing


size


condensation


polymerization),


and


relative


proportions


various


cyclic


oligomers


would


remarkably


change.


fact


ROMP


1.5-


cyclooctadiene,


continuous


series


cyclic


oligomers


(C4H6)n is


formed,


concurrently


with


high


polymer.


This


was


first


noted


1969


using


WCI6/EtAIC


EtOH


as the catalyst and


nce been


observed


with


many


other


catalysts.


This


observation


difficult to


explain


terms


pairwise


mechanism,


can


readily


interpreted


metal-carbene


mechanism


which


propagation


reaction


competition


with


backbiting


reaction.96,97


Final


support


metal


carbene


mechanism


came


from


Casey


isolated
al.99 e


and


and


extendedd


Burkhardt's


showed
Casey


work.98


metathesis


and


which


reaction


Burkhardt's


metal


with


findings


carbene


olefin.
1976,


was


Katz
when


105







polymerization


cyclooctene


with


incorporation


initial


alkylidene


into the polymer


chain.


Development


Lewis


Acid-Free


Metathesis


Catalysts


The


metal carbene mechanism


structure


moiety
reaction


finding


shows that the metal


responsible


directed


olefin


researchers


away


alkylidene
metathesis


from


poorly


defined


and


less


understood


classical


catalysts


and


towards


synthesis


well-defined


transition


metal


alkylidene


complexes


that


directly
classical


catalyze


meta


olefin


catalyst


metathesis


systems,


reaction.


metal


complex


reacts


with


co-catalyst


usually


Lewis


acid)


produce


metal


alkylidene


initial


stage


metathesis


reaction.


Well-


defined
olefin
early v


meta


metathes
vell-defin


carbene
;is reactic
led yet


complexes


without


relatively


however
Lewis


native


can
acid


catalysts


directly


catalyze


co-catalyst.


The


known


Fischer-type


carbene


complexes


and


characterized


presence of heteroatoms (O, N,


S) bonded to the carbene carbon


, such


as (CO)5Mo=C(OPh)Me,100 (CO)5W=C(OMe)Ph,101 (CO)4W


=C(OMe)-


(CH2)2CH


=CH


Such Fischer carbene complexes do not normally


initiate


olefin


metathesis


reaction


because


they


both


coordinately


and


electronically


saturated.


They


can


sometimes
(CO)5W=


, however,
C(OMe)Ph)


be
, or


activated


reaction


metathesis


with


heating


co-catalyst


(e.g.,
(e.g.,


Ih ~ a h\ ,a- .. a ~ lrIr


a a l~ a n a. a*l


-,.


S I SI -. I -l n S 151 '1 *Rn ...* Sn It I' *a fie a flU' 1' a *. ai a a a..aA ~






then


available


coordination


olefin


and


subsequent


metathesis


intermediate


metallacyclobutane.


Since


reaction


Fischer


directly,


carbene


chemists


complexes


have


cannot


searched


initiate


metal


metathesis


alkylidenes


with


both


coordinately


and


electronically


unsaturated


structures


that


could


directly


catalyze


metathesis


reaction.


The


first


such


carbene complex was obtained by Ofele,103 and since then


a variety


of synthetic routes for alkylidene complexes,


LnM=CR1R2 (R1


R2=


alkyl


aryl)


have been discovered.104


Some of these complexes are


good


initiators


exchange


olefin


metathesis


and


metathesis


polymerization


absence


Lewis


acid


example


such


complex


W(=CHCMe3)(OCH2CMe3)2Br2,105 formally a


12-electron


species,
prior to


which


reaction.


readily


The


able


comply


exes


coordinate


with


substrate


HCMe3)(NAr)(OR)


olefin


106-108


(Ar=2

(CF3)


,6-C6H3


and


Pr2;


OR=0-2,6-


W(=CHCMe3)(CH


C6H3-i-I

2CMe3)


Pr2,


OCMe2(CF3),


C1109


OCMe


4-coordinate,


electron-deficient,


complex,


active


Re(=CHCMe3)(NAr)


metathesis.


2(OR)


The


(OR


rhenium-carbene


-2,6-C6H3-


OCH(CF3)2),110 which is also


4-coordinate,


however


native


metathesis


reactions


because


it has


electron


count


(if the


lone pairs on each nitrogen are counted).


metal


Among
carbene


well-defined,


complexes,


coordinative


high


oxidation


electron-deficient


and


four


coordinate


Schrock's


tungsten


and


molybdenum


alkylidenes


(Figure


f the type


M(CHR')(NAr)(OR)2


(M=W,


1.17)106,108,111,11 2 ,















Ft. *.0~


Figure


1.17


Highly


reactive


Lewis


acid-free


Schrock


alkylidene.


The


early


work


metal


carbene


complexes


suggests that the


best


catalytic


meta


alkylidene


should


have


highest


possible


oxidation


state


and


owest


coordination


number.1 13


A 4-coordinate


VIB transition metal (W


Mo) complex could only be obtained by using


OXO


or i


mido


ligand


, of which


the oxo


was discarded


because


could


provide


stabilizing


steric


bulk


complex.


aromatic


mido


ligand,


such


N-2,6-C6H3-i-Pr2


has been used in


Schrock's


prevents


catalysts


because


deactivation


provides

catalyst


necessary


through


bulk


that


ntermolecular


dimerization.


114


The


activity


Schrock


alkylidene


W(CH-t-Bu)(NAr)(OR)2


metathesis


olefins


depends


critically


upon


nature


substituent


example,


tungsten


complex


which


OR=


OCCH3(CF3)2


an active catalyst for the metathesis of ordinary


olefins


at a rate that may be as high as


turnovers/min


at 25


in a hydrocarbon solvent,


a a ~.J :


whereas analogous OR


-.: at


* a
* a a a *


=(O-t-Bu) complexes


n a aa- -a a t ala flig, ar .. -:*ll -C -.n4


11~f


M R' No

W t-Bu _a
W CMe2Ph 1
Mo CMe2Ph le


rA A k~


*1 A *L II I







alkoxides


more


electrophilic


metal


center,


thus


more


stable


metallacyclobutane


formed


metathesis


reaction.


The


very


highly


electron


withdrawing


alkoxide


ligand


OR=O(CF3)2CF2CF


2CF3


however,


form a too stable and relatively


un reactive


conversion.


metallacycle


and


explanation


, consequently
for the above


cause


reactivity


metathesis


change with


nature


groups


that the


nucleophilic


attack


of the


olefin


metal to


form


a metallacyclobutane


is a rate determining


step


metathesi


reaction.


The


alkylidene


reactivity
igand size.


Schrock


catalyst


also


related


The neopentylidene [=CHC(CH3)3] catalyst can


100 times less reactive than the propylidene (=CHCH2CH3) analog,


more


stable


than


less


bulky


counterpart.1 06


The


igands


catalysts


were


optima


selected


based


their


contributions


activities


and


stabilities


catalysts


The


X-ray


M(CHR')(NAr)(OR)


studies


2(M=W,


4-coordinate


complexes


Ar=2,6-C6H3-i-Pr2


R'=CMe2Ph,


type
t-Bu)


show


them


alkylidene


pseudotetrahedra


substituent


N/W/C


complexes


plane


which


points toward the


imido


nitrogen


atom


(syn


rotamer).


It has


been


suggested


that syn


and


rotamers


both


accessible


(anti


referring


rotamer


which


alkylidene


substituent


points


away


from


imido


nitrogen


atom)


and


some


cases


, have


been


served


interconvert


with


activation


barrier


about


kcal.1 16


The


metallacycle


W[CH(Me3


)CHCH2](NAr)[OCMe(CF3)2]2 has been







equatorial


plane.


Square-pyramidal


(ST)


tungstacyclobutane


observable


for the


least


active catalysts


(OR=O-t-Bu).11


Schrock


alkylidenes


readily


react with


aldehyde


, carbonyl,


and


ester


groups


through


a Wittig-type


reaction


(Figure


1.18)


, forming


meta


oxide


thus


resulting


deactivation


of the catalysts.1 18


[M] HR +


R'CHO


[M] ==


RCH==CHR'


Figure


1.18.


Wittig-type
aldehyde.


reaction


between


Schrock


alkylidene


and


Molybdenum


complexes


appear


more


tolerant


functionalities


than


tungsten


complexes.


The


less


electrophilic


molybdenum


a higher


catalysts


selectivity which


incorporated


ROMP


demonstrate


allowed


lower


numerous


polymers.


metathetic


functional


example,


activity


groups to


monomers,


which


contain


ether,


ester


amide,


nitrile,


and


thioether,


have


been


polymerized


through


ROMP


techniques.


118


Molybdenum complexes,


however


more


readily


decomposed


than


their


tungsten


analogs


through


by a 1-hydride


rearrangement


mechanism


and


metallacyclobutane


bimolecular


coupling


complexes
alkylidene


ligands,


especially


methylidenes.


119


As Figure


1.19 shows


, Mo(CH-


t-Bu)(NAr)[OCMe(CF3)212


reacts


with


excess


ethylene


give


trigonal-bipyramidal


Mo(CH2CH2CH


2)(NAr)[OCMe(CF3)2]2


which


allowed to decompose in the presence of


excess


ethylene and yields


an unstable


molybdenacyclopentane


complex


Mo(NAr)-







tungsten


catalysts


polymerizing


functionalized


monomers,1 11


but are also less stable


n the presence of


excess


ethylene.119


NAr


ROII


+ xs CH2=CH2


SCH-t-Bu


NAr
FO- l!b>
no-kr


+ xs CH2=CF


-I-


'-
2E -
*RO-l


NAr


Figure


1.19.


Decomposition of Mo catalyst in presence of


excess


ethylene.



Ring Opening Metathesis Polymerization (ROMP) and


Acetvylene


Metathesis


Polvmeri


action


The


first


ring


opening


metathes


polymerization


was


conducted


195765


and


involved


metathesis


reaction


cyclopentene


and


norbornene


MoO3/AI


203,


which was


activated


with


LiAIH4 (Figure


1.20).


This was followed by other academic and


industrial
commercial


search


polymers


new


have


been


unsaturated
produced


polymers.


ring


Several
opening


polymerization


was


first


using


commercial


classic


product


catalysts.
prepared


Trans-poly(norbornene)


RuCI3


catalyzed


Cat.


Cat.






polymerization
poly(octenamer)


norbornene


was


prepared


1976.


120


polymerization


Next


trans-


cyclooctene.121


The


polymerizability


cyclic


monomer


greatly


depends


ring strain.


The strain


is high for 3- and 4-membered rings because


of the high degree of angle strain and is also high for 8-


and 10-


membered


rings


because


of the crowding


strain


of the


rings.


Ring


strain


and


7-membered


rings


and


sign


of the


free


energy


change


(AG)


for the


polymerization


process


is sensitive


number


physical


factors:


monomer


concentration


temperature,


and


pressure.


very


large


rings


containing


negligible


strain,


transitional


reaction


entropy


entropy
polymer.


driven


through


gain


There


competitive


reactions


ring


opening


metathesis


polymerization:


linear


propagation


producing


high


molecular


weight


polymer


and


cyclization


producing


series


cyclic oligomers.


The


mechanism for


near propagation


ROMP


shown


Figure


where


trans


ition


meta


alkylidene


R'HC-- --R-=- [M]


[M]=CHR'


[M]-CHR'


R'HC-(=-


=[M]


R'HC-= -R-= [M]







(carbene),


[M]=CHR'


reacts


with


cycloalkene


form


metallacyclobutane


intermediate.


The


metallacyclobutane


then


cleaves


produce


new


metal


alkylidene


containing


one


repeat


unit.


The


new


meta


alkylidene


continues


reacting


with


more


cycloalkenes


through


metallacyclobutane


form


high


molecular


weight


polymer.


Cyclization


happens


through


backbiting


intramolecular


metathesis


reaction


while


chain


propagation


proceeding


(Figure


1.22).


The formation of cycloalkene in


ROMP


often observed


such


yielding


octadiene


cyclohexene


2.8-decadiene


and


metathesis


polymerization


trans-1,5-cyclodecadiene.


B [Mt)=


UC~zMtj


Figure


Formation
metathesis


cyclic


reaction


oligomers
123


intramolecular


Ring


opening


metathesis


polymerization


"living"


polymerization


reaction


, becau


metal


alkylidene


remains


attached to


the growing end


of the


polymer chain


(see


Figure


1.22).


"Living"


refers


nonterminated


polymerization


which


propagation


species


remain


active


reaction


stage.


The


giving


polymerization


produces


polymers


having


a narrow


molecular weight


distribution


(c.a.


<1.1)


and


molecular


weight


polymer


depends


ratio


monomer to


initiator


concentrations.


Living


00







certain


order.124


unique


class


living


polymerization


catalysts


for the


Lewis


ring


opening


acid-free


The


first


tran


iving


metathesis


sition


ring


meta


polymerization a
alkylidenes.114


opening


metathesis


highly


polymerization


active


was


reported


complexes


Grubbs


and


and


norbornen


Tumas125
ie (Figure


1984


1.23).


using


titanacyclobutane


Schrock-type


alkylidenes


such


M(CH-t-Bu)(NAr)(OR)2 (M=W,


Mo)114 are ideal for controlled


iving


polymerization


since


they


relatively


unreactive


toward


the acyclic C=C bonds along the polymer backbone, but are extremely


reactive


towards


strained


cyclic


olefins,


even


temperatures.


Cp2Ti


65 C


Figure


1.23.


First


living


opening


metathesis


polymerization.


Ring


opening


metathesis


polymerization


very


useful


preparing


polyacetylenes


and


oligomers--polyenes


through


precursors
Feast128


direct


ring


discovered


opening


that


polymerization.1 14,


tricyclo[4


25.128


2,0]deca-3,7,9-triene


134


and


related


molecules


ring-opened


classical


olefin


metathesis


catalysts


give


polymer


from


which


arene


ejected


upon


heating


produce


polyacetylene


(Figure


1.24).


Knoll


and


Schrockl35


have


reported


preparation


tert-butyl


capped


polyenes containing


up to


15 double


bonds,


where polymerization of







terminated


transition


meta


pivaldehyde

alkylidene


Wittig-like


carbonyl


reaction


between


group.


Figure


1.24.


Preparation


polyacetylene


from


8-bis


(trifluoro-


methyl)tricyclo[4


,2,2


,0]deca-3


,7,9-triene.


Polyacetylenes


obtained


from


metathesi


polymerization


substituted


acetylene


transition


metal


catalysts


have


attracted


significant


interest


chemists


since


1970s.


The


metathesis


reactions


acetylene


nduced


metal


carbene


catalysts


into


three


categories:1 36


138


cyclotrimerization


(Figure


, (a)) ,


polymerization


(Figure


, (b))


and


exchange


metathesis


(Figure


, (c)).


3 MeC=CH


n Ph=CH


Me Me


=CPh-CH n
'n


2 EtC-CMe


EtC-CEt


MeCsCMe


Figure


Three


categories


acetylene


metathesis


reaction.


I. S I~~I S .I - --I -


F.


I


1


|


I,


I







polymerization


process,


metallacyclobutene


formed


combination of an alkylidene and acetylene triple bond,


which is then


cleaved to form a double bond adjacent to the alkylidene on the end


of the chain (Figure


1.26).65


Poly(methylacetylene),


poly(butylacetylene)


and


poly(pheny


acetylene)


can


obtained


through


metathesis


polymerization


corresponding


monosubstituted


acetylene


using


RR'C=W(CO)3,


R
C CH


[M] --CR


R
P !C
aI
Pn-c

\//=
1- -l
V\]i C
"R


Figure


1.26.


Propagation of polymerization


of acetylene by a


metal


carbene chain


carrier.


WC


6/ROH


MoCI5


catalysts


139-141


Disubstituted


polyacetylenes


can


synthesized


using


catalysts


such


RR'C


=W(CO)3 and


metathesis


WCI6/Ph4Sn


polymerization


since


ving


acetylene


polymerization,


block


copolymers


can


monomers


readily


particular


produced
sequential


controlled


order


Schlund


addition


al.144


reported


triblock


Bu)(NAr)(O-t-Bu)


copolymer


was


obtained


when


was treated with 50 equiv of norbornene,


W(CH-t-
then 3-


9 equiv of acetylene, and then 50 equiv of norbornene.






Acvclic


Diene


Metathesis


(ADMET)


Polymerization


One of the


most significant successes


metathesis chemistry


development


acyclic


diene


metathesis


(ADMET)


polymerization


which


extends


metathesis


polymerization


new


area.


Early


metathesis


polymerizations


include


ring


opening


metathesis


polymerization


(ROMP)


and


acetylene


metathesis


polymerization.


The


former


very


usefu


polymerization


method


and


produces


variety


unsatu rated


polymers,


which


some


have


become commercial


products.


The


atter is


limited to obtaining


only


polyacetylenes
polymerization


and


related


method


copoiymers.


produced


numerous


The


new


different


ADMET


unsaturated


polymers,


many of which are difficult to obtain


by any other method.


Acyclic


diene


metathesi


polymerization


step,


condensation,


equ


brium


polymerization.


This


potential


polymerization


method


was


first


attempted


early


1970,


with


little


success.


145


-14


Dall'Asta


Ul 4


were


first to


report


attempted


polymerization


hexadiene


and


1.4-


pentadiene


catalyst.


using
During


classic


meta


reaction


catalysts


, only


with


linear


Lewis


acid


unsaturated


a co-


oligomers


were


obtained


and


ethylene


was


released.


Other


early


attempts


Doyle146
classical


and
Lewi


Zuech


acidic


al. 14


catalyst;


further c
s would


demonstrated


that


catalyze


the
step


polymerization


produce


high


molecular weight


polymer.


1987


, Lindmark-Hamberg


and


Wagener


re-investigated






reaction


Through


produced


a carefu


molecular


analysis of the


weight


reaction


metathesis


products,


they


polymers.
discovered


that


vinyl


addition


competed


with


metathesis


, leading


mixture


products


and


failure


produce


high


molecular


weight


metathesis


polymer.


The


Lewis


acid


co-catalyst


was


responsible


cationic


chain


propagation


that


produced


vinyl


addition


products,


including


crosslinking


polymer.


obtain


further


evidence


competing


reactions


between


vinyl
and


addition


and


co-workers


metathesis


designed


condensation


and


carried


polymerization,


elegant


Wagener


model


studies149-150


using


styrene


and


substituted


styrenes


reagents


and


WCI6/EtAICI2


as the catalyst.


Only the cationic polymerization


product,


polystyrene,


was


obtained


(Figure


1.27),


which


indicated


that


catalyst


used


metathesis


reaction


catalyzes


cationic


vinyl


addition


reactions


WCI6/EtAICI2


W(CHCMe3)(NAr)[OCH3(CF3)2]2



+ Ethylene


Vinyl


Addition


Product


Metathesis


Product


Figure


Model


studies


cationic


vinyl


addition


with


classic


Lewis


acidic


catalyst


system


and


metathesis






Step


and


chain


addition


polymerization


have


significantly


different


various


molecu


mechanisms


reaction


events


almost


Polymerization


occurs


basically
Chain


immediately


terms


polymerization


after


propagation


time-scale


produces
reaction


reactive


polymer
begins.
species


through
molecul


successive


to a chain.


, rapid addition


Therefore,


large


numbers of monomer


high molecular weight polymers are


formed as soon as the polymerization


has started.


Step


polymerization


proceeds


stepwise


reaction


between


functional


groups


reactants


, and


size


molecules


increases


relatively


slow


rate.


Reaction


proceeds


slowly


from


monomer


dimer


, trimer


tetramer


, and


until


eventually


large


polymer


molecules


formed


Therefore,


monomers disappear


early


reaction


stag


and


high


molecular


weight


molecules


form


at the


final


stage when


reaching


a very


high


monomer


conversion.


small


molecule


synthesis


reaction


considered


success


90%


conversion


achieved.


contrast,


a conversion


greater


than


99%


needed


step


polymerization


produce


high


molecular


weight


polymer


The


relationship between conversion
described by Carothers equation:
Xn=


where


and degree of polymerization can be
.2


1/(1-p)


Xn is the number average degree of polymerization and p is the


extent of conversion of the functional group.


(Figure


A plot of this equation


1.28) reveals the need for high conversion of monomer(> 99%)






200


0.95
0.99
0.995


10
20
100
200


0.00


1.00


Figure


1.28.


Variation


molecular weight


with


conversion


equilibrium


step


polymerization.


ADMET


polymerization


need


high


conversion


monomers


met


elimination


vinyl


addition


reactions,


which can


be achieved by using Lewis acid-free


metal alkylidenes as


metathesis


catalysts.


their


model


study


metathesis


reaction


styrene


with


Schrock's


tungsten


catalyst,


Wagener


and


co-workers


found


that


stilbene


was


only


resulting


product


and


trace of viny


Those


addition


model


product was produced149,150


studies


way


(see


successful


Figure
ADMET


polymerization.


The


first


high


molecular


weight


polymer


was


produced


polyoctenamer,


the A
using


\DMET


tungste


polymerization
n catalyst W


1,9-decadiene


(CH-t-Bu)(N-2,6-C6H3


Pr2)[OCME(CF3)22. 149,150


Further research has demonstrated that


a variety


unsaturated


polymers,


including


those containing






The


mechanism


ADMET


polym


erization


shown


Figure


1.29,


where


original


alkylidene


(e.g.,


neopentylidene)


reacts with


terminal


then


olefin


cleaved


, forming


monomer-type


metallacyclobutane


(step


metallalkylidene


which


a small


olefin


molecule


(step


Advancing


clockwise,


monomer-type


LnM=CR2


R2C=CH2


02H4






LnM


M=CH


Reacting


with


monomer or polymer

SX


/H
LnM=C
\ H


x


X~


x ~


w I


..








metallalkylidene is


reacted with


a second


monomer to


form


a dimer-


type


cyclobutane


(step


and


produ


ces


dimer


and


metallamethylidene


(step 4).


Through


the continuous cycle of


steps


molecule


chain


grows


high


molecular


weight


polymer.
evacuated


Sma


molecules


continuously


that


push


produced


equ


reaction


brium


polymerization


forward.


unsaturated


polymers


containing


different


functionalities


have


been


produced


using


both


tungsten


and


molybdenum catalysts,


it has been found that the molybdenum based


catalyst


seems


more


tolerant


functionalized


diene


than


tungsten


analog.


Brzezinska and Wagener151


-153 discovered that a


series


ether-containing


enes


could


ADMET


polymerized


ether-containing


unsaturated


polymers


S


uch


ether-containing


polymers can only be produced with the monomers,


CH2=


CH-(CH2)n-


O-(CH


)n-CH


=CH2


which


have


number


methylene


groups


between oxygen and olefin


equa


to or greater than


2 (n>2).


Divinyl


ether


(n=0)


metathesis


and


reaction


diallyl
when


ether


(n=1)


catalyzed


polymerize


neopentylidene


tungsten


catalyst.


Similar


results


observed


when


using


molybdenum


neopentylidene,


diallyl
linear


ether


except


that


produced


this


brium


condition


mixture


, polymerization
2,5-dihydofuran


oligomers.1 53


Following


this


ether


search,


Wagener


and






polymerization


correspondent


functionalized


monomers.


The


unsaturated


polycarbosilanes157


, polycarbosiloxanes158


and sulfur


containing
polymerization


polymers1 59


well.


have


Random


been syr
copolymers


ithesized

containing


ADMET


octenylene


and


butenylene


a statistical


array


based on


feed


ratio


have


been


obtained


from


copolymerization


1.9-decadiene


and


1,5-


hexadiene


160


The


block


poly(1,4-phenylenevinylene-co-


octenamers)


have


been


obtained


through


copolymerization


1,4-


dipropenylbenzene


1.9-decadiene.161


Study on the Chemistry of Conjugated Monomers


n ADMET


Polymerization


Since


1988,


successful


number


ADMET


unsaturated


polymerization


polymers,


was


first


such


achieved


ether


ester


ketone,


carbonate,


silane


and


thioether


containing


polym


have


been


new


successfully


polymerization


synthesized


method.


from


This


different


dissertation


monomers


describes


through


a study


reactivities


conjugated


monomers


ADMET


polymerization


an effort to extend this polymerization area.


The monomers used are


those


which


conjugated


polyacetylene,


olefins


phenylene g

poly(phenylene


directly


;roup


The


vinylene),


and


conjugated


polymers


their


together


produced


derivatives,


which


potentially


useful


as conducting


and


nonlinear


optical


materials.


nnn; Inn~n U


Al *nh


n~~,n~nrA an +hke ef mr


c~fllrl\l


hVnlhvh rl


nl~~,,,,r






2,4-hexadiene


and


2,4,6-octatriene


bulk


and


solution


conditions.


The


reactivites


1,3-butadiene


and


1,3,5-hexatriene


examined.


Copolymerization


2,4-hexadiene


and


2,10-dodecadiene


conducted at room temperature.


Telechelic


polymerization


polyacetylenes
f 2,4-hexadiene


synthes


with


ized


internal


through


ADMET


monoolefins.


The


ADMET


polymerization


and


copolymerization


and


1,3-


dipropenylbenzene


conducted


room


temperature


using


molybdenum


catalyst.












CHAPTER 2
EXPERIMENTAL



Instrumentation


Proton nuclear magnetic resonance (NMR) 200 MHz,


magnetic resonance 50 MHz,


13C nuclear


and solid state carbon NMR spectra were


obtained


with


Varian


XL-200


series


NMR


Surperconducting


Spectrometer


system.


Chloroform-d


(CDCI3)


benzene-d6


purchased


from


Aldrich


was


directly


used


solvent


without


further


purification.


NMR


metathesis


reaction


solvent


benzene-


was


purified


with


calcium


hydride


and


sodium


mirror


eliminate


reported


moisture


and


parts


oxygen.


million


proton


down


field


chemical


from


shifts


tetramethyl


were


silane


(TMS),


and


carbon


chemical


shifts


reported


were


internally


referenced


CDCI3


or benzene-d6.


Quantitative


13C


NMR


spectra


were


8-12


with


pulse


delay


10-20


sec.


Ultraviolet


analyses


were


performed


Perkin-Elmer


Lambda


UV/Vis/NIR


spectrophotomete r


chloroform


with


solvent.


scanning


Gas


rate


chromatography


was


nm/min


and


carried


Hewlett


Packard


5880A


series


equipped


with


detector


and


fused silica 0.31


. . .. .


m caDillarv column


Dacked with a 0.17


. .






Elemental


analyses


compounds


were


performed


Atlantic


Microlab


Norcross,


Georgia,


Department


Chemistry,


University


Florida.


Gel permeation chromatography (GPC) was carried on a


Waters


Associates


iquid


chromatography


apparatus


equipped


with


U6K


injector


and


differential


refractometor


and


Perkin-Elmer


LC-75


ultraviolet


(uV)


spectrophotometric


detector


Phenomenex


x 30 cm crosslinked


polystyrene-divinylbenzene


columns,


A and


500A


or 500


A and


5000


were


used.


The


mobile phase was HPLC grade tetrahydrofuran (THF) at a flow rate of


mL/min.


The


calibration


curve


molecular


weight


calculation


was


obtained


from


polybutadiene


standard


samples


(Polysciences,


Inc.)


with


molecular


weight


distribution


smaller


than


1.07


Polymer


samples


were


dissolved


THF


and


filtered,


then


injected


to examine the retention time.


data were collected and analyzed


a Zenith


personal


computer


mode


equipped


with


Metrabyte


multi-IO


card


Reaaents


and


Purification


Three


different types


Lewis


acid


free


metal


catalysts


were


used in this study: W(CHCMe3)(N


,6-C6H3-i-Pr2)[OCH3(CF3)2]2 1a;


W(CHCMe2Ph)(N-2,6-C6H3-i-Pr2)[OCH3(CF3)2]2 Ib; Mo(CHCMe2Ph)-


-2.6


-C6H3


-i-Pr


2)[OCH3(CF3)


structures


catalysts,


page


, Figure


1.17).


These


three


catalysts


were






Since


sensitive


metathes


procedures.


well-defined,


traces


reaction


The


Lewis


moisture


were


volatile


acid-free


and


carefully


iquid


metal


oxygen


purified


reagents


were


catalysts


reagents


using
stirred


very


used


following


over


calcium


hydride in a round bottom flask stoppered with a drying tube unti


evolution


of hydrogen gas was observed.


This predried


reagent was


degassed by at least three freeze-thaw cycles on a high vacuum line,


then


transferred


under


vacuum


sodium


mirrored


flask


and


stirred


unti


reaction


impurities


with


sodium


was


longer


evident.


After


dryness


absence


oxygen


were


accomplished,


reagent


was


transferred


vacuum


flask


and


sealed


with


RotoflowTM valve.


Reagents reacted with sodium, such as 4-pentene-


acetate


and


3-butenal


diethyl


acetal,


were


dried


only


through


calcium


hydride


procedure


described


above


and


carefully


degassed


minimum


freeze-thaw


cycles.


Non-volatile


liquid reagents were heated under high vacuum for removal of oxygen


and


moisture.


Solid


reagents


were


sublimed


under vacuum


ensure dryness and absence of oxygen.


n-Pentane


was


washed


with


concentrated


sulfuric


acid


least


three


times


there


was


further


coloration


observed.


was


then


washed


with


KMnO4


n 3 M H2SO4 three


followed


aqueous


NaHCO3 and water several


times to ensure the


acid


was


rinsed


out.


The


pentane


was


then


dried


over


calcium


hydride


and


distilled


flask


containing


sodium


potassium


amalgam.


This


n-pentane


was


refluxed


kety


under


argon


before






3M


Tetrahydrofuran


and


ether


were


dried


refluxing


over


sodium/potassium


benzophenone


ketyl


and


under


argon


protection


Other


solvents


were


reagent


HPLC


grade


and


redisti


before


reaction.


General ADMET


Reaction


Techniaues


metath


esls


reactions


and


polymerizations


were


conducted


a cus


tomary


ADMET


apparatus,


149


which


a high


vacuum


system


made


glass


shop


University


Florida.


This


vacuum


was


constructed


entirely


PyrexTM


and


consis


rotary


pump


conjunction


with


diffu


sion


pump.


High


vacuum


PyrexTM ground


glass


joints


were


used


various


junctions


permit


evacuation


reaction


vesse


and


tran


solvents


and


reagents


from


one


vessel


another


The


entire


system


was


evacuated


and


dried


thoroughly


with


a torch


remove


traces


adsorbed


water


vapor


and


oxygen


from


surface


glass.


The


system


then


was


checked


presence


pinholes


with


Tesla


high


voltage


discharge


round


bottom


flask


equipped


with


a high


vacuum


RotoflowTM


valve


was


used


metath


esis


reactions


and


polymerization


The


reactions


were


conducted


a temperature


range


gas


trap


and


a dry


ce-isopropanol


condenser


were


connected


with


reaction


that


ethylene


butene


produced


metathesis


reaction


could


collected


and


removed.


(10-6




41

NMR Solution Reactions


order to


obtain


intimate


detail


metathesis


reactions,


NMR


solution


benzene-d6


reactions


reagents


were


and


performed
catalysts


NMR


tube


Generally,


containing


nert


atmosphere,


catalyst,


Mo(CHCMe2Ph)(N


-2,6-C6H3-/-


Pr2)[OCCH3(CF3)2]2,


was dissolved in 0.5 mL of benzene-d6 in a NMR


tube


, and 20 to 50 mg of reagent was then added to the solution.


The


tube was sealed by the NMR cap.
1H and 13C NMR spectroscopy.


The reaction was then monitored by


ADMET


Polymerization of


2.4-Hexadiene


Monomer


2.4-hexadiene


was


purchased


from


Aldrich


Chemical


trans, trans,


Company,
trans,cis,


purity,


and


cis, cis


which


mixture


isomers.


Bulk


Polymerization


2.4-Hexadiene


The


polyacetylene


oligomer


was


synthesized


through


bulk


ADMET


polymerization


2,4-hexadiene


following


procedure.


n an


argon-filled dry box


, 1.0 g


mmol)


of purified 2,4-hexadiene


and


(0.025


mmol)


Schrock's


tungsten


catalyst


(mole


ratio


monomer


catalyst,


490:1)


were


weighed


and


mixed


round


bottom


flask.


The


reaction


mixture


was


stirred,


sealed,


and


+Tha nnrmihm rv;n n tnvtf rnarriar ni it


~ k n Y\ mhr ihrl ~n n I in ni I I I m F I I ir )h M






generated


from


reaction


were


removed


intermittent


application


high


vacuum


drive


equilibrium


reaction


forward.


The polyacetylene oligomer solid was formed


in 5 min


the reaction was continued for 1


h before quenching by exposure to


The


polymer


was


added


chloroform


(swelling


and


partially


soluble) and precipitated


methanol,


then filtered and dried.


It had


following


yield


and


spectral


properties:


yield


72%


Molecular weight


integration of 1H NMR


Mn=240


D.P.=8


GPC


Mn=420


Mw=580


, Mw/Mn=


1.39


1H NMR


(200 MHz,


CDCI3)


1.76 (d, 6 H, CH3)


5.60-5.85


4 H, CH=CH)


6.0-6.5 (br


conjugated ene)


13C NMR


(50 MHz,


CDC13), 6


17.8,


17.9,


18.6


125.8


126.3
130.6


128.6
130.7


132.5


129.3
130.8
132.8


129.5
131.6


132.9


129.6
131.8


130.1


130.4


131.9


133.1


133.3


, 130.5,
, 132.3,
, 133.4,


133.5


, 133.6,


133.7


, 133.8,


133.9


UV (nm,


CHCI3)


, 303,


317


332


, 349


, 380


, 404


423


order to collect and characterize


released


butene gas


during


metathesis


polymerization,


NMR


tube


was


connected


reaction flask.


After enough gas was trapped by


liquid


nitrogen


tube


was


removed


and


immediately


filled


with


chloroform-d


then


sealed with


a NMR


cap.


The


2-butene was then


characterized


1H and 13C


NMR spectroscopy.


The


NMR spectra


showed


80% of


trans isomer for the 2-butene produced.


It had the







1H NMR


(200 MHz, C6D6), 6


1.51 (d


, CH3 cis),


1.59


(d, 6 H,


CH3


trans)


5.39 (m,


-CH=CH-


, trans),


5.48 (m,


13C NMR


2 H,


-CH=CH-


(50 MHz, C6D6)


126.0 (-CH=CH-


, cis)


.4 (CH3 cis),


, cis)


17.9 (CH3, trans),


.6 ( -CH=CH-,


After


polyacetylene


was


precipitated


methanol,


remaining


solids


dissolved


methano


were


obtained


evaporation


solvents


and


then


characterized


NMR


spectroscopy.


Low


molecular weight


polyacetylene


and decomposed


catalysts


Solution


were


found.


Polymerization


2.4-Hexadiene


The


polyacetylene


oligomer


was


synthesized


through


solution


ADMET


polymerization


2,4-hexadiene


by the following


procedure.


argon-filled dry


box,


of Schrock's tungsten


catalyst


la (0.025 mmol) and 10 mL of benzene were mixed


na 30


round


bottom


flask.


The
10-3


mixture


was


stirred


until


uniform


catalyst


solution


was


formed.


The


purified


2,4-


hexadiene (1.0 g) was then added to the solution


.2 M) and stirred


immediately.


Polyacetylene


oligomers


started


precipitate


after


min.


The


reaction


was conducted at room


temperature


and


then


quenched


exposure


The


polymer


solution


was


subsequently


added


methano


and


polymer


precipitated,


then was filtered,


and dried


The polyacetylene oligomer 3b had the


trans)













Molecular


weight


Integration


NMR


Mn=420


.=15


GPO


=540


, Mw=800


Mw/Mn=


1.47


1H NMR


(200 MH


, CDCI3)


.76 (d,


6H


, CH3)


, 5.60-5.85


,4H


=CH),


6.0-6.5


conjugated ene)


CHCI3)


364


383


406


, 451


470


Synthesis


and


Polymerization


2.4.6-Octatriene 4


2.4.6-Octatriene


was


synthesized


using


method


reported


literature.


162


Ethylmagnesium


bromide


diethy


ether),


DL-3-butyn


-2-ol


(99%)


, crotoaldehyde


(99+


and


thium


aluminum


hydride


(powder


95+


were


purchased


from


Aldrich


Chemica


Synthesis


Oct-6-ene-3-vne


-2.5-diol 5


The


70 mL


ethylmagn


esium


bromide


in ether


mole)


solution


was


added


a 500


three-neck


round


bottom


flask


with


argon


and


200


toluene


was


then


added


with


stirring.


The


mixture


was


cooled


while


solution


butyn


(7.0


, 0.10


mole)


ether


was


added


stirring


was


continued


room


temperature.


After


mixture


been


cooled


crotoaldehyde


(0.11


mole)


toluene


were


added


, and


mixture


was


stirred


room


temperature;


Addition


original


an ammonium


nsoluble


chloride


VISCOUS


aqueous


complex
solution.


then


dissolved.


isolation






Yield


75.6%


1H NMR


(200 MHz, CDC13), 8


1.45 (d, 3 H, ((C-OH)-CH3)


, 1.75 (d,


3 H,


(=CH)-CH3),


4.2-4.4 (br


2 H


, two -OH)


,4.6 (m


(OH)-CH-(CH3) ),


4.85 (d,


, (=CH)-CH-(OH)),


5.5-5.7


=CH-(CHOH))


13C NMR


(50 MHz, CDCI3)


,4.8-6.0 (m,
17.4 (CH3)


1 H, (CH3)-CH=)


24.0 (CH3)


57.9


62.4 (CH(OH)(C=))


128.4 (CH=)


Synthesis


83.3 (=C), 87.7 (C-),


, 130.1 (=CH).


2.4.6-Octatriene 4


a 500


round


bottom


flask


(0.17


mole)


lithium


aluminum


hydride


was


dissolved


300


diethyl


ether


The


solution was then


cooled down to 0 C.


A second solution of


7.8 g


(0.055
added


mole)


dropwise


oct-6-ene-3-yn


above


e-2,5-diol


lithium


diethyl


aluminum


ether


hydride


was


solution.


After
heated


acid


adding


reflex


and


oct-6-ene-3-yne-2,5-diol,


temperature


evaporation


of the


dried


ether


who


Addition


layer


gave


mixture


aqueous
a residue


was


tartaric


which


was


fraction


distilled


give


2,4,6-octatriene


(1.9


following


yield


and


spectra


properties:


Yield


1H NMR


(200 MHz,


CHC13),


1.75 (dd,


, CH3)


, 5.4-5.8


CH-=-CH


,2 H),


5.9-6.1


(m, CH-=-CH


, 2 H), 6.2-6.6


, CH-=-CH


2 H)


(CH(OH)(C~))







13C NMR


(50 MHz,


CHCl3), 8 13.4 (CH3


cis) ,


18.3 (CH3


trans),


121.9


124.6


, 125.5


125.7


126.5


128.2


128.7


, 129.0


, 129.5


129.6


, 130.5


, 131.8,


132.0


132.6


UV (nm, CHCI3)


269


279


Elemental


Analysis:


Calculated for C8H1


, 88.82; H


11.18


Found


C, 88.68, H,


11.23


Bulk


RaW mnerizabti on


2.4.6-Octatriene 4


The


polyacetylene


oligomer


was


synthesized


through


bulk


ADMET


polymerization


2,4,6-octatriene


n an argon filled dry


box,


1.0 g


(9.3 mmol) of


2,4,6-octatriene and 20 mg


(0.026 mmol) of


Schrock's


molybdenum


catalyst


were


weighed


(mole


ratio


monomer to catalyst, 350:1) and mixed in a round bottom flask.


The


reaction


flask


was


stirred


sealed


and


then


moved


vacuum


system.


The


polymerization


was


carried


room


temperature


with


stirring.


The


small


molecu


generated


from


reaction


were


removed


intermittent


application


vacuum.


The


polyacetylene

continued for 1


solid


was


formed


min.


The


h and quenched by exposure to air.


reaction


was


The polymer was


dissolved


chloroform


swelling


and


partia


soluble),


precipitated


methanol,


then


filtered


and


dried.


had


following


yield


and


spectral


properties:


yield


69.4%


I~~, t.... I Ii LI i


.I A Aa


- .~ a


IM *Z BLIUI I U J 1


LIAIAAII)AL







1H NMR


(200 MHz,


CDCI3)


1.75 (d,


, CH3), 5.55-5.80


,4 H)


6.0-6.8 (br, conjugated ene)


13CNMR


(50 MHz,


130.6


CDCI3), 8


, 130


131.9


18.3


132.0


(CH3, trans)


132.3


129.3


, 132.4,


, 129.8,


, 132.8,


132.9


, 132.8,


133.0


133.3


, 133.4


UV (nm,


CHCI3)


290


380


404


423


AttemDted


ADMET


Polymerization


1.3-Butadiene 6


Monomer


1,3-butadiene


was


purchased


from


Aldrich


Chemical


Company,


It was 99+


pure


and was


packaged in a


steel


cylinder.


order


minate


possible


moisture


and


oxygen


, monomer


was


vacuum condensed


a sodium


mirrored


flask and sealed at room temperature for


2 h before use.


Atte m noted


Bulk


Polymerization


1.3-Butadiene 6


A 25


RotoflowTM


valve-sealed


reaction


flask,


containing


mg (0.039 mmol) of molybdenum catalyst ic and a magnetic bar, was


connected


sodium-mirrored


flask


pre-stored


with


gram


monomer


6 (18 mmol).


This system was then set up to the vacuum


and


monomer


was


vacuum


transferred


reaction


flask.


The


reaction


was


conducted


RotoflowTM


valve-sealed


reaction


flask


room


temperature


polyacetylene


polymer


was


observed


The


un reacted


monomer


was


then


FI I-


t-ii- -


-- -~_I -m -. I- t -.-A -


r


_ r


_- _-







solids


remaining


in the


reaction


flask


were


examined


13C


NMR


spectroscopy.


The


reaction


was


repeated


reaction


time


4 h.


NMR


Reaction


.3-Butadiene


Molybdenum


catalyst 1 c


an argon-filled


, 20


(0.37


mmol)


1,3-butadiene,


(0.039


mmol)


molybdenum


catalyst


and 0.5 mL of C6D6


were


NMR


mixed


tube


a vial


and


The


sealed


mixture


then


was


immediately


characterized


transferred


13C


NMR


spectroscopy


reaction


times


JO


9 days.


Attempted


ADMET


Polvmeriz


action


1.3.5-Hexatriene


Monomer


3.5-


hexatriene


was


purchased


from


Aldrich


Chemical Company


, as 97% pure.


Attempted


Bulk


Polvme


rization


.3.5-Hexatriene


same


procedure


polymer


zation


3-butadiene


was


owed.


The


reaction


was


conducted


in a round


bottom


flask


with


mixture


1.3.5-hexatriene


and


tungsten


catalyst


sma


portion


monomer


reacted


with


catalyst.


After


evaporation


un reacted


monomer


, the


remaining


were


washed


with


methanol.


insoluble


crosslinked


polymer


was




49

NMR Reaction of 1.3.5-Hexatriene and Molybdenum Catalyst ic


The same procedure for the NMR reaction of 1,3-butadiene was


followed


and


1,3,5-Hexatriene,


molybdenum


catalyst


1c, and 0.5 mL of C6D6


were


used


reaction.


The


solution


was


characterized


1H and


13C


NMR


spectroscopy


reaction times: 0.5 h


Synthesis


10 h


and


36 h


and 56 h.


Polvmerization


2.10-Dodecadiene 9


Synthesis


1,8-octylenebis(triphenylphosphonium


bromide) 8


The


were


1.8-dibromooctane


purchased


from


Aldrich


(98%)


and


Chemical


triphenylphosphine


Company


and


(99%)
used


directly


without


further


purification.


solution


40.8


(0.15


mole)


1,8-dibromooctane


triphenylphosphine


400


and


86.5


(0.33


dimethylformamide


was


mole)

heated


reflex


temperature


with


stirring


The


solution


was


then


allowed


diethyl


cool


ether


precipitated


room


with


from


temperature


stirring.

solution


and


was


white


and


filtered,


owly


stal


washed


poured


solid


with


ether,


was


and


dried


vacuum


room


temperature.


The


weight


compound


was


had


following


yield


and


spectral


properties:


Yield


91.9%


Il IL I cf L LI f


c'nnen~


lu hlhlD


~ Un\


I rinn hn u,


A


1







Synthesis


2.10-Dodecadiene 9


Acetaldehyde


and


n-butyllithium


(2.5


solution


hexane)


argon


were


purged


purchased


from


3-necked


Aldrich


flask


Chemical


103


Company


193


mole)


octanylenebis(triphenylpho


sphonium


bromide)


was


added


400


THF


. The


mixture


was


cooled


154.


n-buty


thium


(0.386


mole)


was


slowly


added


mixture


form


ylide.


The


reaction


was


conducted


minutes,


over


which


time


solution


changed


from


faint


yellow


cherry


as the


mixture


was


allowed


warm


room


temperature.


After


room


temperature,


reaction


mixture


was


cooled


and


THF


solution


(0.405


mole)


acetaldehyde


was


added


dropwise


mixture


over


a period


then


heated


a sli


reflux


The


reaction


was


quenched


with


aqueous


NaHCO3


(5g/L)


extracted


with


ether


. The


ether


ayer


was


dried,


and


evaporated


and


crude


product


was


fraction


dist


owing


yield


and


spectral


properties:


Yield


.97%


1HNMR


200 MHz


,CDC3)


1.23-1.51


8H


, CH3),


2.04 (t,


5.41(m


=CH)


13C NMR


, CDC3),


Trans


isomer:


.8 (CH3)


.2 (CH2),


29.6


(CH


32.6 (CH


,124.5 (CH


, 131.6 (CH=)


Cis isomer


.6 (CH3)


26.8 (CH


29.1


(CH2


29.5 (CH2)


, 123.5 (CH=),


130.8 (CH=)


a"^ i aS& aIJL


rl,,,,r,


4~


n~F7


II l-u ~' rrl


Ir






Polymerization


1 0-Dodecadiene 9


Methyl-terminated


poly(octenamer)


was


obtained


through


ADMET


polymerization


10-Dodecadiene


In an argon-filled dry


,0.5 g


mmol)


compound 2. and


(0.013


mmol)


molybdenum


catalyst


was


added to


a reaction flask,


which


was


then


vacuum


line.


The


reaction


was conducted with


stirring


until


reaction


mixture


solidified


The


solid


polymer


was


then


dissolved


chloroform


and


precipitated


methanol.


The


white


powder


methy


-terminated


poly(octenamer)


was obtained.

Yield


It had the following yield and spectral properties:

81.4%


Molecular weight


integration of


1H NMR


Mn=2810


GPC


Mn=2450,


Mw=3190,


Mw/Mn=


1.31


1H NMR


(200 MHz,


CDCI3)


1.30(br, 8 H,


CH2),


1.63


, CH3),


1.96 (br


, CH2)


5.37 (t,


4 H, CH=CH)


13CNMR


(50 MHz, CDCI3)


18.3 (CH3)


.6, 29.4,


29.6, 30.0,


30.1


33.0


124.9


130.3


132.0


Syntheses


Poly(acetylene-co-octenamers)


AttemDted


Copolvmerization


2.4-Hexadiene


and


1.9-Decadiene 11


The


1,9-decadiene


was


purchased


from


Aldrich


Chemical


Company,


nc, as 989


pure and was dried over calcium hydride and a


enrlii im


mirrnr


carnnn..illor4 nv


hew


n 097


*I


(A CA


mmnlI


*I I| -J






(0.023


mmol)


catalyst


were


mixed


round


bottom


flask.


The


reaction


was conducted


a vacuum


at room


temperature


with


stirring.


The


metathesis


initially and stopped gradually


reaction


n 30 min.


(bubbling)
After 24 h


was


observed


, another 20 mg


of catalyst was added
gradually stopped in 3


Again


0 mmin.


metathesis reaction was observed and
After a total of 48 hours, the unreacted


monomers


were


evaporated


and


remaining


solid


was


characterized


NMR


spectroscopy.


Only


poly(octenamer)


oligomer


was found.


Synthesis


Poly(acetylene-co-octenamer)


Ratio 1 2


argon-filled dry box,


0.16 g


(2.0


mmol)


2.4-hexadiene


and


0.33


(2.0


mmol)


10-dodecadiene


were


mixed


a 4


vial.


The mixture was then added to a 30 mL round bottom reaction


flask


which contained


0.026


mmol)


molybdenum catalyst


The reaction flask was then sealed and moved to a vacuum line.


Polymerization


butene


was


generated


application
solidified,


vacuum.


copolymer


carried


with


reaction


After the


was


was


reaction


dissolved


stirring,


removed


mixture


chloroform,


and


intermittent


was completely


precipitated


methanol,


then


filtered


and


dried


a vacuum.


had


following


yield


and


spectral


properties:


Yield


70.3%


Molecular weight


integration of 1H NMR


Mn=1090


Mn=1090.


Mw=1440


Mw/Mn=1.31


GPC







1H NMR


(200 MHz, CDCI3), 8


1.20-1.55


CH2),


1.63 (d,


CH3)


1.76 (d,


CH3)


, 1.88-2.27


CH2), 5.38


(m, nonconj.,


CH=CH),


5.48-5.82 (m, conj.


CH=CH),


5.93-6.45


13C NMR


(50 MHz,


, (m, conj.
CDCI3), 8


CH=CH)


18.1


29.2


, 29.5


, 29.6,


29.8,


32.8, 33.0, 33.1


, 124.7,


130.1


, 130.6


, 130.8,


131.0,


131.9


, 132.6,


132.7


133.


134.7


135.3


135.4


UV (CHCI3, nm)


, 248, 273


284


305


320


, 335, 353,


382


Synthesis


,408,


Polv(acetvlene-co-octenamer)


this


synthesis,


same


procedure


ratio


copolymerization


was


followed


The


mole


ratio


2.4-hexadiene


(0.092 g) to


10-dodecadiene (0.365 g) was


The copolymer 13


following


yield


and


spectral


properties:


Yield


69.9%


Molecular weight


integration of 1H NMR


1510


GPC


Mn=1420


, Mw=2140


Mw/Mn=1.50


1HNMR


(200 MHz, CDCI3)


1.22-1.52


CH2)


, 1.64 (d,


CH3)


1.76 (d, CH3)


1.88-2


, ( m, CH2), 5.39


,internal CH=CH) 5.48-5.80,


con'


. CH


5.92-6.30


conj. CH=)


13CNMR


(50 MHz,


CDCl3) 5


18.1


29.2


29.6


, 29.8,


32.8, 33.0, 33.1,


125.8,


128.8


, 130.1


, 130.3,


130.5,


lOAD


404 n


40- (11


4i000C


100lr


--5


10A 7


( m,


Ratio '3


(m


1~E'1


II'IEA


|






Synthesis


Polv(acetylene-co-octenamer)


Ratio 14


this


synthesis,


same


procedure


ratio


copolymerization


was


followed.


The


mole


ratio


2,4-hexadiene


(0.052 g) to


10-dodecadiene (0.421


g) was


The copolymer 14


following


yield


and


spectral


properties:


Yield


68.9%


Molecular weight


Integration of 1H NMR


Mn=


1340


GPO


Mn=1 580,


Mw=2450


Mw/Mn=


1.55


1H NMR


(200 MHz, CDCI3), 8


.22-


1.52


, CH2)


, 1.64 (d,


CH3)


1.76 (d,


CH3)


1.88


-2.27


, ( m, CH2)


5.39


internal CH


5.93-6.28


=CH) 5.48-5.82,


, (m, conj


conj. CH=CH),


. CH=CH)


13C NMR


(50 MHz, CDC13), 6


17.9


29.0


29.3


29.4


, 29.6,


32.6,


32.8,


124.5,


130.3,


130.8


, 131.6,


132.4


UV (CHCI3,


236


283


, 320


, 335


353


408


Synthesis


Poly(acetvlene-co-octenamer)


BatiLQ


this


synthesis,


same


procedure


ratio


copolymerization


was


followed


The


mole


ratio


2,4-hexadiene


(0.230 g) to


10-dodecadiene (0.232 g) was


The copolymer had


following


yield


and


spectral


properties:


Yield


66.4%


Molecular weight


integration of 1H NMR


Mn=730


GPC


Mn=560, Mw=660, Mw/Mn=1.18







1H NMR


(200 MHz, CDCI3), 5


1.14-1.49


, CH2),


1.63 (d,


CH3)


1.78 (d,


CH3)


1.83-2.18


CH2)


, 5.38


(br, internal CH=CH) 5.48-5.88,


, conj. CH=CH),


5.93-6.45


, (m, conj.


CH=CH)


UV (CHCI3, nm)


236


305


, 333


352


, 406


Synthesis


Polv(acetylene-co-octenamer)


Bafro -6


this


synthesis,


same


procedure


ratio


copolymerization


was


followed


The


mole


ratio


2,4-hexadiene


(0.328 g)


2,10-dodecadiene (0.166 g)


was 4:1


The copolymer


following


yield


and


spectral


properties:


Yield


62.6%


Molecular weight


integration of


1H NMR


540


Mn=530, Mw=660, Mw/Mn=1.25


1H NMR


(200 MHz, CDC13)


1.10-1.51


, CH2)


, 1.63 (d,


CH3)


1.78 (d, CH3)


1.86-2.26


CH2)


5.38


(br, internal CH=CH) 5.46-5.82,


conj. CH


=CH),


5.82-6.50


, (m, conj. CH=CH)


UV (CHCI3, nm)


274


305


332


352


380


406


Attempted


Polvm


erizalion


c's-


1.4-Dicvano-


1.3-butadiene 1 7


Cis,cis-1,4-dicyano-1,3-butadiene
i I & Jl I i fl .. I- -- __ I N --^ -.. ...


(mucononitrile)
I -- -^ 11 0 a -


was


14 :n


GEC


,(m


m






Attempted


Solution


Polymerization


cis.cis-1.4-Dicvano-1,3-butadiene 1 7


Compound


17 (0.104 g) was added into a 50 mL round bottom


flask


and


sublimed


heating


under


vacuum


remove


moisture


and oxygen.


The flask was then moved


nto a dry box,


and 10 mL of


benzene and 20 mg of catalyst ic were added to the flask.


After 48


reaction


room


tempe


rature


with


stirring,


benzene


was


evaporated


and


remaining


solids


were


characterized


NMR


spectroscopy.


The


unreacted


monomer


was


found


remaining


solids,


without


observing


polymers.


NMR


Reaction of


cis. cia.


1,4-Dicvano-1, 3-butadiene 1 7


argon-filled


cis,cis-


1,4-dicyano-1,3-


butadiene (purified by


ublimation)


was dissolved


in 0.5


mL of C6D6


a vial,


and 30


of molybdenum catalyst


was then added to


solution


and


stirred.


The


solution


was


immediately


transferred


a NMR


tube


characterized


NMR


spectroscopy


reaction


time 10 min


30 min


Attempted


and 16 h.


Polvmerization


trans.trans-1 .4-DiDhenvl-


1.3-butadiene 18


The


trans,trans-1 ,4-dipheny


1,3-butadiene


(mucononitrile)


18 was purchased from Matheson Coleman & Bell, as 98% pure.


It is






Attempted


Solution


Polymerization


trans.trans-1 ,4-D iDhenv


1,3-butadiene 1 8


this


reaction


, the


same


procedure


used


solution


polymerization


cis.c


,4-dicyano-1,3-butadiene


was


followed.


The


unreacted


monomer


was found


remaining


solids,


without


observing


polymers.


NMR Reaction of trans.trans-1 .4-Diphenyl-1 .3-butadiene 1 8


In this reaction


same


procedure used for NMR


reaction


cis,cis-1,4-dicyano-1,3-butadiene


was


followed.


The


reaction


was characterized by NMR spectroscopy at reaction times


10 min, 30


mmi,


1h,


,4h, 6h,


and 16 h.


Synthesis


sobutvI-Terminated


Polvoctenamer 20


Telechelic


polyoctenamer


was


obtained


through


ADMET


polymerization


1.9-decadiene


and


terminal


monoolefin


methyl-l-pentene


19 (Aldrich Chemical Company,


, 98% pure)


argon-filled


box,


0.690


(5.00


mmol)


1.9-


decadiene,


0.082


(1.00


mmol)


4-methyl-1 -pentene


and


(0.01


mmol)


of tungsten


catalyst


were mixed


in a round bottom


reaction


flask.


The


reaction


was


then


conducted


with


stirring


room


temperature


and


ethylene


generated


reaction


was


removed


intermittent


application


a vacuum.


The






filtered,


and


then


dried


under


a vacuum.


It had


following


yield


and


spectra


properties:


Yield


54.9%


Molecular weight


Integration of 1H NMR


Mn=1240


1HNMR


(200 MHz,


CDCI3), 5


0.87 (d


, CH3),


1.2-1.4


, CH2)


, 1.59 (m,


, CH),


1.81


4 H


, CH2)


, 5.38 (m,


, internal olefin)


13C NMR


(50 MHz, CDCI3), 8


28.5


, 29.0


, 29.6,


32.6,


36.4,


42.0


128.9


130.3


131.5


Atte m ted


Polymerization


2.4-Hexadiene


with


4-Methyl-1


-oenten


Attempted


Bulk


Polymerization


2.4-Hexadiene


with


4-Methyl-1 -Dentene


Bulk


polymerization


2.4-hexadiene


with


monoolefin


methyl-1-pentene
polyacetylene.


was


conducted


argon-filled


order to


box,


obtain


0.656


isopropyl-capped


(8.00


mmol)


4-hexadiene,


0.336


(4.00


mmol)


4-methyl-i-pentene,


(0.026


round


mmol)

bottom


molybdenum


flask.


The


catalyst


reaction


were


was


mixed


conducted


together


with


stirring


room


temperature on


vacuum


After 64


liquid


(mainly


containing


NMR


un reacted
spectroscopy


monomers)


and


was


GC/mass


evaporated


and


spectrometer.


characterized


The


remaining


solids were examined by NMR spectroscopy.







NMR


Reaction of


4-Hexadiene and 4-Methyl-l-pentene


with


Molybdenum


Catalyst ic


The


regular


procedure


NMR


reaction


was


followed


reaction.


The


2,4-hexadiene


(0.220


mmol)


4-methyl-1-pentene


(0.430


mmol)


, molybdenum


catalyst


(0.039


mmol),


and


benzene-


d6 (0.500 mL) were mixed


n a NMR tube,


which was then sealed and


monitored by NMR spectroscopy at reaction times


15 mm


30 min


, 60


and 24 h


Metathesis


Coupling


Reaction


Functionalized


Terminal


Olefins


Attempted


Metathesis


Coupling


Ally


Chloride 21


Ally


chloride


was


purchased


from


Aldrich


Chemical


Company,


as 99% pure


argon-filled


mmol)


allyl


chloride


and


(0.026


mmol)


molybdenum


catalyst


were


mixed


round


bottom


reaction


flask.


The


reaction


was


conducted


room


temperature


with


stirring


vacuum


After


stirring,


solution


was


characterized


by NMR spectroscopy, which


showed no coupling product.


Attem ted


Metathesis


Couolina


Allvl


Amine


amine


, as 99% pure.


was purchased from


Aldrich


Chemical


The same procedure for the coupling


Company,

reaction of


.~~~~I S .S S -S1- -S


*


II Il


*


i m


* *


* |


A A






and


20.0


(0.026


mmol)


molybdenum


catalyst


were


used.


After 48 h of stirring, compound


remained


unreacted.


Attempted Metathesis


Coupling


3-Butenal


Diether


Acefli 23


3-Butenal


diether


acetal


was


purchased


from


Aldrich


Chemical Company,


nc., as 97% pure.


The same procedure for the


coupling


reaction


allyl


chloride


was


followed


and


(6.9


mmol)


allyl


catalyst


were


amine


used.


and


(0.026


After


mmol)


stirring,


: molybdenum
compound 23


remained


unreacted.


AttemDted


Metathesis


Coupling


Hexen-2-one 24


5-Hexen-2-one


was


purchased


from


Aldrich


Chemical


Company,


bromide


Inc.,


reaction


98%


was


pure.


followed


The


and


same


procedure


grams


allyl
allyl


mmol)


amine


and


(0.026


mmol)


molybdenum


catalyst


were


used.


After 48 h of stirring, the compound 24


remained


unreacted.


Metathesis


Coupling


4-Methvl-l-pentene 19


The


compound


2,7-dimethyl-4-octene


was obtained through


metathe


coupling


reaction


4-methyl-1-pentane


n an


argon
(0.026


filled


box,


mmol)


molybdenum


mmol)


catalyst


compound


were


and


mixed


round


bottom


reaction


flask.


The


flask


was


then


moved


vacuum






characterized


NMR


spectroscopy.


following


yield


and


spectral


properties:


Yield


99%


1H NMR


(200 MHz,


CDCI3) 8


0.89 (d


, CH3),


1.59


, CH)


1.88 (t,


, CH2),


5.36 (t,


,CH=CH)


13C NMR


(50 MHz,


CDCI3) 5


3 (CH3)


.4 (CH3)


28.5 (CH,


trans)


28.7 (CH


36.4 (CH2


42.1


(CH


trans),


Elemental


129.2 (CH=
Analysis:


, cis) 130


(CH=


, trans)


Calculated for C10H20: C,


85.63; H


14.37.


Found


, 85.45; H,


14.34.


Metathesis


Coupling


4-Penten-1 -vl-acetate


Compound


4-octen-1,8-diy


acetate


was


synthesized


through


metath


esis


coupling


reaction


4-penten-1-yl


acetate


which


was


purchased


from


Aldrich


Chemical


Company,


Inc.,


98%


pure.


The


same


procedure


coupling


reaction


methyl-1-pentene


was


followed,


(7.8


mmol)


compound


and 20 mg (0.026 mmol) of molybdenum catalyst lc were used in


reaction.


The


product 28


following


yield


and


spectral


property


Yield


99%


1H NMR


(200 MHz,


CDCI3) 5


1.68 (m,


, CH2)


, 1.98-2.18


10 H


, CH2 and CH3),


4.05 (t,


, CH2),


13C NMR


5.42 (m,
(50 MHz.


2H,


internal CH=CH)


CDCh )


20.8 (CHt


, -


.4 (CH2)


28.4


S







Elemental


Analysis:


Calculated for C12H2004: C, 63.14; H, 8.83


Found: C, 63.08; H, 8.91


Metathesis


Couolina


Allyltrimethylsilane


Compound


4-bi


s(trimethylsilyl)-2-butene


was


synthesized


through


metathesis


coupling


reaction


allyltrimethy
Company, Ir


silane


which


as 99% pure.


was


The


purchased


from


same procedure


Aldrich


Chemical


for the coupling


reaction


4-methyl-1 -pentene


was


followed


and


(8.8


mmol)


of compound 29 and 20 mg (0.026 mmol) of molybdenum catalyst 1c


were


used


in this


reaction.


The


product 30


following


yield


and


spectra


properties:


Yield


99%


1H NMR


(200 MHz,


CDCI3) 8


0.01 (t,


18H


, CH3)


1.41


4 H CH2)


5.23 (m,


CH=CH


, trans),


13C NMR


5.32 (m,
(50 MHz,


2 H, CH=CH, cis)


CDCI3) 8


1.97 (CH3)


, 1.98 (CH3)


17.8


(CH2,


22.7


(CH2, trans)


123.1


(CH=,


cis),


124.3 (CH=


, trans)


Elemental


Analysis:


Calculated for C10H24S


i2: C,


59.91


12.07


Found: C, 59.90; H,


12.18


~FZL






Syntheses


Telechelic


Polyacetylenes


Synthesis


Hexvl-Terminated


Polvacetvlene


Telechelic

polymerization


polyacetylene


2,4-hexadiene


was

with


synthesized


trans-


through


ADMET


7-tetradecadiene


(Aldrich


Chemical


Company,


98% pure)


argon-filled dry


, 0.328 g


(4.00


mmol)


of 2,4-hexadiene,


0.196 g


(1.00


mmol)


tra n


-tetradecadiene,


and


(0.026


mmol)


molybdenum


catalyst

moved


1c were mixed


vacuum


in a round bottom flask.


line,


and


butene


The flask was then


generated


reaction


was


removed


intermittent


application


vacuum.


The


reaction


was conducted


dissolved


room


chloroform,


temperature

precipitated


for 36


methano


The


, and


product


dried


was


under


vacuum.


t had the


following yield and


spectral


properties:


Yield

Functionality

Molecular weight


68.8%


Integration of 1H NMR


GPC


Mn=340


Mn=330


, Mw=650,


DP=6


Mw/Mn=1.94


1HNMR


(200 MHz,


CDCl3)


0.88 (t, 6 H, CH3),


1.21-1.48


H, CH2)


,1.68 (br


2.08 (m,


4 H, CH2


next to conj. CH=CH)


5.62-6.55 (br


conj.


Synthesis


Isobutvl-Terminated


Polvacetvlene


Telechelic
I S j


polyacetylene


r


fl A I. I


was
S* i *


synthesized


through


ADMET


^ I" i I A __ f l ... .l /'






was followed


, and 0.328 g


(4.00 mmol) of 2,4-hexadiene and 0.140 g


(1.00


mmol)


2,7-dimethyl-4-octene


were


used


reaction.


The product 33
Yield
Functionality


had the following yield and properties:
59.6%
1.6


Molecular weight


Integration of 1H NMR


atC


Mn=790


Mn=290, DP=7


, Mw=1590, Mw/Mn=2.01


1H NMR


(200 MHz, CDCI3)


CH),


2.00 (t,


0.89 (d,


H, CH3),


, CH2), 5.62-6.40 (br, conj.


1.65 (m,
CH=CH)


2H,


Synthesis


Phenvi-Terminated


Polvacetvlene


Telechelic


polyacetylene


was


synthesized


through


ADMET


polymerization of


2,4-hexadiene with


propenylbenzene 34.


The same


procedure
followed.


ynthesis


and


0.328


(4.00


telechelic


mmol)


polyacetylene


2,4-hexadiene


and


was


0.236


(2.00


mmol)


propenylbenzene


were


used


reaction.


The


product 35


Yield
Functionality
Molecular weight


had the following yield and spectral properties:


63.4%


Integration of 1H NMR


GmC


Mn=730,


Mn=340


Mw=1250


DP=7


Mw/Mn


1HNMR


(200 MHz, CDCI3)


5.98-6.65 (br, conj.


CH=CH),


6.65-6.95 (m, 2H, =CH-Ph),


7.16-7.55 (m,


10 H, phenyl)






Synthesis


Trimethylsilvl


Methvlene-Terminated


Polyacetylene 36


Telechelic


polyacetylene


was


synthesized


through


ADMET


polymerization


2,4-hexadiene


with


1.4-b


s(trimethy


butene)


The


same


procedure


synthesis


telechelic


polyacetylene


was


followed,


and


0.328


(4.00


mmol)


2,4-


hexadiene


and


0.200


(1.00


mmol)


1,4-bis(trimethylsilyl


butene) were used in the reaction.


The product 36


had the following


yield


and


spectral


properties:


Yield
Functionality
Molecular weight


57.4%


integration of


1H NMR


Mn=410


DP=9


GPO


Mn=560, Mw=840,


Mw/Mn=1.49


1H NMR


(200 MHz,


CDCl3)


0.2-0.8 (m 18 H, CH3)


1.35


4 H, CH2)


Synthesis


5.65-6.50 (br, conj.


3-vl-Acetate-propyl-Terminated


CH=CH)


Polyacetylene 37


Telechelic


polymerization


polyacetylene


4-hexadiene


was
with


synthesized th
4-Octen-1,8-diy


rough


ADMET


acetate


The same


procedure


for the


synthesis of telechelic polyacetylene


was followed


, and 0.328 g


(4.00 mmol) of 2,4-hexadiene and 0.204 g


(1.00


mmol)


4-Octen-1,8-diyl


acetate


were


used


reaction.


The product


had the following


yield and spectral


properties:


Yield
Functionality


55.4%






1H NMR


(200 MHz,


CDCI3),


1.64 (m 4 H,


CH2)


2.05 (s, 6 H,


CH3)


2.2 (m,


, CH2)


5.60-6.40 (br


conj. CH=CH)


Syntheses and Polymerizations of Dipropenvylbenzenes


Synthesis


1.2-Dipropenylbenzene 39


Phthalic


bromide


(99%)


dicarboxaldehyde


and


n-butyllithium


(98%)


(2.5


ethyltriph
solution


enylphosphonium


hexane)


were


purchased


from


Aldrich


Chemical


Company,


Inc.


Ethyltriphenylphosphonium


500


THF


bromide


argon


0.23


purged


3-neck


mole)
flask.


was


The


added


mixture


(suspension)


was


cooled


and


butyllithium


(0.24


mole)


was


slowly


added


mixture


form


ylide.


The


reaction


was


conducted


changing


from


faint yellow to


warm


room


cherry


temperature.


color


After


mixture was


room


allowed


temperature,


reaction


mixture


was cooled


and


THF


solution


15 g


(0.11


mole) of phthalic dicarboxaldehyde was added dropwise over a


period


, then


stirred


room


temperature


The


reaction was quenched with aqueous NaHCO3 (5g/L),


and the mixture


was


extracted


with


ether.


The


ether


layer


was


then


dried


and


fractionally


distilled


give


pure


product.


It had


following


yield


and


spectral


properties:


Yield







1H NMR


(200 MHz,


CDCI3)


(dd, 6 H, CH3, trans),


1.88


(dd, 6 H, CH3


,5.80 (m, CH=),


6.13 (m


10-7.50 (m,


4 H, phenylene)


13CNMR


(50 MHz,


CDCI3) 8


14.3


(cis),


14.4 (cis)


(trans),


125.3


126.1


126.8


127.5


, 128.9,


129.0


129.3


, 129.5


135.0


, 135


136.3


136.5.


Elemental


Analysis:


Calculated for C1


2H14


,91.08; H,


8.92.


Found: C, 90.80


Synthesis


8.99.


1.3-Dipropenylbenzene 40


The


1,3-dipropenylbenzene


was


synthesized


through


Wittig


reaction


isophthaldehyde


and


ethyltriphenylphosphonium


bromide.


The


same


procedure


synthesis


1,2-dipropenylbenzene


was


followed.


The


product 40


following


yield


and


spectral


property


Yield


35.6%


1HNMR


(200 MHz


CDCI3) 5


1.87 (m


,CH3)


5.78


(m, cis,


=CH-(CH3))


, 6.22


trans


=CH-(CH3)),


6.40


2 H


, CH


=(CH-CH3))


10-7.40 (br


, 4 H, phenylene)


13C NMR


(50 MH


, CDC13) 8


(CH3


18.5 (CH3


trans),


123.6


124.0


124.3


126.5


126.8


128.0


, 128.3


128.6


, 129.4


, 130.0


, 137.5


138.1


Elemental


Analysis:


Calculated for C1


2H14: C


91.08; H


8.92


rF_ aI nhj a7 II fl


cH=),






Synthesis


Poly(1.2-phenylene


vinylene) 41


The


procedure


polymerization


2,4-hexadiene


was


followed.


The reaction was conducted at room temperature using


g (6.3 mmol) of 1,2-dipropenylbenzene 39 and 80 mg (0.094 mmol) of


tungsten


catalyst


The product 41


was


dissolved


chloroform,


precipitated


methanol,


and


dried


under


vacuum.


had


following


yield


and


spectral


properties:


Yield


Molecular weight


Integration of 1H NMR


Mn=870


1HNMR


(200 MHz,


CDCl3) 6


1.84 (d,


, CH3),


6.10


(m, =CH-(CH3))


6.66-6.90 (D


, CH


=(CH-CH3)),


7.08-7.85 (br,


vinylene and phenylene)


13C NMR


(50 MHz, CDCI3) 8


18.8 (CH3)


126.2


, 126.3,


126.5,


, 126.8,


126.9


127.8


127.9


, 128.3,


128.6,


128.8


, 129.0,


129.2,


129.7


136.0


136.5,


136.8


UV (nm, CHCI3)


Broad


236-400,


2 maximum absorption: 278,


328.


Synthesis


Polv(1.3-phenvlene


vinylene) 42


The


vinylene)


same


was


procedure
followed.


synthesis


The


reaction


was


poly(1,2-phenylene


conducted


room


temperature using


1.0 g


(6.3


mmol)


of 1,3-dipropenylbenzene 40 and


20 mg (0.023 mmol) of tungsten catalyst lb.


The product 42 had the


following


yield


and


spectral


properties:







1H NMR


(200 MHz, CDCI3) 8


1.84 (d, 6 H,


CH3)


6.24-6.50


4 H, CH=CH-(CH3))


7.08-7.85


vinylene and phenylene)


UV (nm, CHCI3)


Broad


236-360,


2 maximum absorption: 266,


306.


Synthesis


and


Polymerization


of 8-OctenyI-o-propenyIbenzene 4_4


Synthesis


4-Bromo-1-propenylbenzene 43


this


reaction,


same


procedure


synthesis


dipropenylbenzene


was followed.


The chemical


were purchased


from


Aldrich


Chemica


Company,


Inc.,


and


(0.20


mol)


4-bromobenzaldehyde


(99%),


0.21)


ethyltriphenyl


phosphonium


used


(99%),


in the reaction.


The compound 43


solution


butyllithium


had the following


were


yield and


spectral


properties:


Yield


32.6%


1H NMR


(200 MHz,


CDCI3)


1.85 (d,


, CH3)


5.82 and


6.10-6.41


2 H, cis and trans -CH=CH-)


, phenylene)


7.42 (dd,


7.26


phenylene).


Synthesis


8-Octenyl-p-propenylbenzene 44


argon-filled


and


, 8-octenyl


magnesium


bromide was added dropwise into a


I. a a I.. -


solution of 1


g (63 mmol) of 4-


- -- Afl --aa


-I n nf


'5


,,, I\






Aldrich)


anhydrous


ether.


The


mixture


was


stirred


room


temperature for 1


room


temperature,


and then refluxed for 20


resulting


mixture was


After cooling down
hydrolyzed with 1 M


aqueous


solution


and


extracted


ether


twice.


The


organic


portion was collected, and the ether was then removed under reduced


pressure.


The


fraction


distillation


mixture


gave


pure


product of 4.54 g.


It had the following yield and spectral


properties:


Yield


31.4%


1H NMR


(200 MHz,


CDCl3) 5


1.20-1.51


, CH2),


1.51-78


, CH2),


1.88 (d,


3 H, CH3)


2.04 (q,


, CH2)


2 H, CH2)


,4.94 (m,


, =CH2)


5.78 and 6.08-6.50


13CNMR


(m, 3 H,
(50 MHz,


-CH=)


,7.3-7.48 (m,


CDCl3) 6


4 H, phenylene)


(CH3, cis)


, 18.45 (CH3,trans),


28.9, 29.0, 29.1,


31.4


, 33.8


, 35.6, 35.7


124.6


126.0


128.1


128.5


129.8


, 130.9,


135.0


135.4


, 139.1,


141.1,


141.4


Elemental


Analysis:


Calculated for C17H24: C,


89.41; H


10.59


Found


,89.26; H


, 10.67


Polymerization


8-Octen l-p-propenyl benzene 44


Poly(hexamethylene


p-phenylene


vinylene)


was


obtained


through


The


ADMET

same


polymerization


procedure


8-octenyl-p-propenylbenzene


polymerization


dipropenylbenzene


was


followed.


The


reaction


was


conducted


room


temperature


usina


(4.4


mmol


- fl -l


8-octenyl-p-


44.






Yield


72.5%


Molecular weight


Integration of 1H NMR


Mn=1890


1HNMR


(200 MHz,


CDCl3) 6


1.21-1.45


, CH2)


1.45-1.65


CH2),
CH2),


1.83 (d, 6 H, CH3),


2.56 (t, CH2)


, 5.36 (m,


1.85-2.3 (br


CH=CH)


CH2)


6.18


CH=CH)


6.32 (m,


CH=CH)


7.03-7.46


phenylene and vinylene)


13C NMR


(50 MHz,


CDCl3) 5


18.4


(CH3)


28.8


29.0


, 29.1


29.4,
126.1


29.5, 31.4,


126.3


33.0


128.5


, 35.6,
. 128.7


124.6


, 125.6,


129.6


129.


125.8,
7, 130.0,


130.1


130.3


130.9


, 135.4,


141.5


Syntheses of Polv(phenvlenevinvylene-co-octenamers)


Synthesis


Polv(1


phenvlenevinvlene-co-octenamer)


RatQo fi


argon-filled


box,


0.316


(2.00


mmol)


1,3-


dipropenylbenzene,


0.276 g


(2.00


mmol) of 1,9-decadiene and 20


(0.026
round


mmol)

bottom


molybdenum


reaction flask.


catalyst


were


mixed


a 30


Polymerization was carried on at 30 C


with


stirring


and


small


molecu


generated


reaction


were


removed


intermittent


application


vacuum.


After


reaction


mixture


was


solidified,


chloroform


was


added


dissolve


mixture.


The


copolymer


was


then


precipitated


methanol


and






Yield


Molecular weight


GPC


Mn=1090,


Mw=1440


, Mw/Mn=1.31


1H NMR


(200 MHz, CDCI3), 8


.20-1.55


, CH2)


, 1.63 (d,


CH3)


1.76 (d, CH3)


1.88-2.


( m, CH2), 5.38


(m, nonconj.,


5.93-6.45


CH= CH) 5.48-5.82, (m, conj. CH=CH),


conj. CH=CH)


13C NMR


(50 MHz,


CDCI3) 8


18.1


, 29.2


, 29.5,


29.6


, 29.8,


32.8, 33.0, 33.1


131.9


130.1


, 132


, 130.6,


, 134


130.8,


135.3


131.0,


, 135.4


UV (CHC13, nm)


Broad


236-350


Synthesis


Polv(1


phenylenevinylene-co-octenamer)


Ratio 47


this


synthesis


same


procedure


ratio


copolymerization


was


followed.


The


mole


ratio


dipropenylbenzene (0.632 g) to


1,9-decadiene (0.138 g) was 4:1


. The


copolymer


had the


following


yield and spectral properties:


Yield


63.4%


Molecular weight


GPO


Mn=670


Mw=830


Mw/Mn=1.25


1H NMR


(200 MHz, CDCI3)


1.20-1.65


1.90(d,


CH2),


2.23 (d,


CH2)


6.10


, (m, conj.


CH=CH), 6.70,


13C NMR


(m, conj.
(50 MHz,


7.10-7.80 (phenylene)


CDCl3) 6


18.8


29.1


29.6


33.3


33.4


, 126.3,


126.4


, 128.8,


128.9,


129.0,


129.5


133.1


, 133.0,


134.2


, 135.4,


135.8,


136.4,


(m


=cH)




73



Synthesis of Poly(1.2-phenylenevinylene-co-octenamer)


Ratio 48


this


synthesis,


same


procedure


ratio


copolymerization


was


followed.


The


mole


ratio


dipropenylbenzene (0.158 g) to


copolymer


1,9-decadiene (0.552 g) was


had the following yield and spectra


Yield


The


properties:


66.3%


Molecular weight

1H NMR (200 M


GPO


Hz, CDCI3)


Mw=4040


1.20-1.65


Mw/Mn=


, 1.65 (s


1.97

I, CH2)


1.85-2.10 (br


, CH2)


2,20 (s,


CH2), 5.38


(s, nonconj., CH=CH),


6.15-6.45


conj


CH=CH),


7.15-7.35


(phenylene)


13C NMR


(50 MHz,


CDC13) 8


27.2


29.0


, 29.6


29.7


32.6


, 33.0,


123.6.124.4


128.6


129.7


129.9


, 130.3


, 131


138.1


UV (CHCI3, nm)


Broad


236-290


Synthesis of Poly(octenamer-co-1.2-phenylenevinylene) 49


argon-filled


0.276


(2.00


mmol)


1,9-


decadiene and


15 mg


(0.020 mmol)


of molybdenum catalyst 1c were


mixed


round


bottom


reaction


flask.


The


reaction


flask


was


then


sealed


and


moved


vacuum


line.


Polymerization


was


carried


room


temperature.


After


solid


polyoctenamer


was


4n~~~~~ rmtr A4 r. 'at rnnt 4n 0 'hnt -' rd rr +n


In A


(m,


Cn YMh rl


S II


nrlrlnrl ~n


n


mmhl\


1*1^1 Ir


-J


#' ,I






room


temperature.


The


copolymer was


dissolved


chloroform,


precipitated


from


methanol,


and dried


under


vacuum.


It had


following


yield


and


spectral


properties:


Yield


Molecular weight


atC


Mn=1780


Mw=4080


Mw/Mn


1H NMR


(200 MHz, CDCI3)


1.20-1.60


, CH2)


, 1.65 (d,


CH2)


1.88 (d,


CH3),


2.23 (d,


CH2), 5.38 (s, nonconj.,


CH=CH),


6.15-6.45


, (m, conj.


CH=CH)


, 7.10 (s,


vinylene),


13-7.60


, phenylene)


13CNMR


(50 MHz,


CDCl3) 8


18.5


, 27


, 28.7


, 29.0


29.2


, 29.3,


29.5,

124.6

130.3


29.6,


, 124.9,

, 130.4,


, 32.6,


125.0

131.0,


33.0

25.2.


131.1


123.5


125.6

131.5.


, 123.6,

128.7.


137.5


129.6


, 138.1


, 124.4,

, 129.7,

138.3


UV (CHCI3,


Synthesis


nm)


Block


Broad


Rolh~i


236-350.


phenylenevinylene-co-octenamer) 50


argon-filled


box,


0.32


(2.0


mmol)


dipropenylbenzene


and


(0.020


mmol)


molybdenum catalyst


1c were mixed in a 30 mL round bottom reaction flask.


The reaction


flask


was


then


sealed


and


moved to a


vacuum


Polymerization


was


carried


room


temperature


with


stirring.


After


poly(1


phenylenevinylene)


was formed


, 0.276 g


(2.0


mmol)


1,9-decadiene


was


then


added


into


poly(1


,2-phenylene


vinylene)


and


polymerization


coDolvme


was


tt


continued


was


dissolved


room


* .


chloroform.


temperature.


orecioitated


The


from






Yield


63.6%


Molecular weight


GPO


Mn=


1400,


Mw=2300,


Mw/Mn=


1.65


1H NMR


(200 MHz, CDCI3)


1.20-1.60


, CH2)


, 1.65 (s,


CH2),


1.95 (s CH2)


2.20 (


, CH2)


5.38 (s,


nonconj.,


CH=CH),


6.00-6.20


, (br,


coni


.CH=CH)


6.70


conj. CH=CH),


7.10-


7.65


(vinylene and


phenylene)


13C NMR


(50 MHz,


CDCI3) 8


29.0,


29.3


, 29.4


29.5


29.6


29.7


, 32.6,


33.3


33.4


126.3


, 126.9,


28.1


128.3


128.5


128.7


, 129.0


129.5


129.7


, 130.3,


134.0


134.1


135.5


UV (CHCl3, nm)


Broad


6-390


Synthesis of Poly(1 .3-phenylenevinylene-co-octenamer)


Ratio 51


this


synthesis


same


procedure


synthesis


poly(1


,2-pheny


enevinylene-co-octenamer)


was


followed.


The


mole


ratio


1,3-dipropenylbenzene


(0.316


1.9-decadiene


6 g)


was


The copolymer


following


yield


and


spectral


properties:


Yield


Molecular weight


GPO


Mn=


1240


Mw=1720


Mw/Mn=1.39


1H NMR


(200 MHz, CDC13)


1.20-1.60


, CH2)


, 1.65 (d, CH2),


1.85-2.10 (br,


2.23


CH2), 5.38


nonconj., CH=CH)


6.05, (m, con


j. CH=CH)


6.65, (m, conj. CH=CH),


10-7.70 (phenylene)






13CNMR


(50 MHz, CDCI3) 8


28.5,


28.7


, 28.8,


29.0,


29.1


29.4


, 29.6, 29.8


32.6


, 33.1, 33.3,


125.3,


125.8,


126.0,


126.3


126.8


128.3


128.4

130.3


128.8


130.4


128.9


32.4


129.0


129.4


133.1


129.5

133.3


129.7
134.0


129.9


135.5


, 135.8,


136.8


UV (CHCI3,


Broad


236-350.


Synthesis of Poly(l.3-phenylenevinylene-co-octenamer)


Ratio


this


synthesis,


same


procedure


synthesis


poly(1


,2-phenylenevinylene-co-octenamer)


was


followed.


The


mole


ratio


1,3-dipropenylbenzene


(0.632


1,9-decadiene


(0.138 g)

spectral


was


4:1
a


properties:


Yield


64.3%


Molecular weight


GR3


Mn=610


Mw=790


Mw/Mn=


1.30


1H NMR


(200 MHz, CDCI3)


(br, CH2)


2.23 (t, CH2)


1.30-1.65


6.15-6.50 (m,


1.85-2.00


conj. CH=CH),


(50 MHz,


vinylene)
CDCI3) 6


18.5


29.1


29.3


33.0


123.6


124.1


124.3


124.8


124.9


, 125


125.3


125.7


126.1


128.5


128.6


129.0


129.6


, 129.8


130.9


131.0


131.5


, 137.4


137.5


, 137


, 138.0


138.3


The copolymer


following


yield


and


7.10


13C NMR


(phenylene)




77


Synthesis of Poly(1.3-phenylenevinylene-co-octenamer)
1:4 Ratio 53


synthesis,


poly(1


same


procedure


,2-phenylenevinylene-co-octenam


synthesis


was followed.


The


mole


ratio


1,3-dipropenylbenzene


(0.158


1.9-decadiene


(0.552


was


The


copolymer


following


yield


and


spectral


properties:


Yield


67.6%


Molecular weight


1H NMR


GR3


(200 MHz, CDCI3)


Mn=2640


Mw=5790


1.20-1.60


Mw/Mn


, 1.65 (d,


CH2),


1.85-2.10 (br


(s, nonconj


CH2), 2.20 (m,


CH=CH)


CH2),


6.10-6.45, (m


5.38


conj. CH=CH),


(phenylene)


13CNMR


(50 MHz,


CDCI3) 6


29.0


29.4


29.6


32.6


, 33.0,


123.6


124.4


128.6


, 129


, 129.8,


130.3,


131.1


138.1


UV (CHCI3, nm)


Broad


236-290


Metathesis Reaction of Prooenvlbenzene and 1-Nonene


In an argon-filled dry box, a mixture of propenylbenzene 54 and


1-nonene


were


mixed


a 4


vial.


The


total


weight


of the


mixture was


0.5 g,


and the


mole


ratios of


compound


54 to 55


were


100:0


90:1


75:25


, 50:50,


, 10:90, and 0:100,


respectively.


The


.5 .- -- -l- A a 5


--1-I--i


*


* -


,,,. a a


tinnEr


__


.1.


,L A


Irl __i


L






The


reaction


was


carried


room


temperature


with


stirring,


and


ethylene,


removed


propene,
intermittent


and


butene


application


generated


a vacuum.


reaction


After


was


reaction


was


completed,


mixture


products


was


characterized


NMR


spectroscopy.


The


products,


stilbene


-phenyl-1


-nonene


and


8-hexadecene


had the fo


owing


NMR


resonances.


1H NMR (200 MH


, CDCI3)


Stilbene


7.10


7.55


phenyl)


-Pheny


-nonene


CH3),


.15-1


.6 (br


, CH


2.20


6.13-6.46 (m,


7.40


, phenyl)


8-Hexadecene


CH3)


.15-1.6


1.97


5.38 (m,


=CH)


-CH),


~CH)










CHAPTER 3

REACTIVITIES OF CONJUGATED DIENES AND TRIENES
IN ADMET POLYMERIZATION


Since


acyclic


diene


metathesis


(ADMET)


chemistry


was


first


established


new


equ


brium


, step,


condensation


polymerization


1988,


many


high


molecular


weight


unsaturated


polymers


and


copolymers
polymerization.


149-159


have


been


Prior to this dissertation


synthesized


through


monomers used


ADMET


n ADMET


polymerization


have


possessed


a spacer


group


between


olefins


n Figure 3.1).


Cat.


CH2=CH2


Figure 3.1.


Acyclic diene metathesis


(ADMET) polymerization.


This


research


studies


reactivitie


conjugated


dienes


spacer


group)


and


trienes


ADMET


polymerization


using


Schrock's


well-defined


directly


metal


conjugated


alkylidene


catalysts


together


been


monomer


studied


having


previous


olefins


ADMET


research.


meaningful to


broadening


examine


scope


chemistry


ADMET


polymerization,


conjugated


dienes


~R~-X;F~







Internal


conjugated


monomers


CH3 group at each end), 2,4-


hexadiene


and


2,4,6-octatriene,


and


terminal


conjugated


monomers


(two


hydrogen


hexatriene


were


atoms


used.


each


The


end)


different


, 1,3-butadiene


reactivities


and


between


1,3,5-


internal


conjugated
investigated


monomers


The


and


terminal


conjugated


copolymerization


monomers


2,4-hexadiene


were


and


nonconjugated dienes was also examined.


The


Polymerization


Chemistry


.=...r ... ln ni It .o.n e i


n ines


internal


conjugated


diene


2,4-hexadiene


was the


first


monomer


examining


polymerizability


conjugated


dienes.


The


2,4-hexadiene


was


selected


because


was


commercially


available


liquid,


and


it was easy to


purify


comparison to


gaseous


1,3-butadiene.


The


ADMET


polymerization


2.4-hexadiene


was


rapid,


and the


polymer


obtained was


a conjugated


methyl-terminated


polyacetylene


(Figure


3.2).


Cat.


C \ nCH3
CH3- vn


Figure 3


ADMET


polymerization of


2,4-hexadiene.


According


reaction


general


cycle


ADMET


polymerization


polymerization


2,4-hexadiene


mechanism


could


described as in Figure 3.3.


One double bond of 2,4-hexadiene reacted


I ntn rn a I


r. nnilrna tpy(













Step


+
LnM=CHC(CH3)2Ph


Step 2



CH3CH=CHC(CH3)2Ph


C4H8 is removed







LnM


Reacting


LnM=C H


Step 6


Step 5


with


monomer or polymer


Step 3


Step 4


/H
L M=C
CH3


Figure 3.3.


The ADMET


polymerization cycle for


4-hexadiene.






with


initial


metal


alkylidene


form


metallacyclobutane


(Figure


alkylidene


, Step


and


which


neophyl


then


was


alkene


rearranged


(Step


This


form


alkyliden


second
e then


reacted with the olefin


moiety of another monomer to


form a second


metallacyclobutane


which


then


was


rearranged


dimer


and


third


meta


alkylidene


continued


(Steps


a cycle


(Steps


and
3-6)


The


obtain


reaction


onger


process


chain


was


molecules


and to release 2-butene.


this


ADMET


polymerization


product,


2-butene


was


collected


mixture


trans


and


isomers,


respectively,


generation


as determined


2-butene


NMR


was


spectroscopy


evidence


(Figure 3.4).


demonstrate


The


that


polymerization


was


metathesis


condensation


reaction.


The


polyacetylene


product,


was


molecular


weight


gomer


and


was


characterized


NMR


spectroscopy


using


chloroform-d


solvent.


The


NMR


spectra


of these


polyacetylene


oligomers


(Figure


3.5)


clearly


showed


that


methyl


groups


were


present at both ends of the polyacetylene chain.


The protons of the


terminal


methyl


groups


were


ppm


and


protons


conjugated


double


bonds


were


found


mainly


between


6.0-6.4


ppm.


The peak near 5.7 ppm was assigned to the protons of the conjugated


double bonds at the ends of the polyacetylene chain


Solid state


13C


NMR


spectroscopy


also


confirmed


existence


this


polyacetylene's


structure.










(trans)


1
2 (trans)
2

2 (cis)


(cis)


a,. *j .1177 1 .l S*pw S. '' p1 ~~TTI UI I


* I'l I


140


120


100


20 ppm


Figure 3.4.


13C NMR spectrum of 2-butene collected


n ADMET


polymerization


2.4-hexadiene.


3 1

H3C pCH3
"a ^ 2


7 6 5 4 3 2 ppm


3 1


CH3


H3C


j~ r. rur rII Ir r r rI h I


-I .2 .* r w r r 9- ^


-. .


ppm


Fiaure 3.5.


1H NMR spectra of


2,4-hexadiene and its bulk


1I" "1 ''' "r i


_


---


l I l I I I I


----- -- -- --


I i,


n






According


NMR


integration


values,


polyacetylene


oligomers


fro m


bulk


polymerization


2,4-hexadiene


were


average


6-10


repeat


units.


Since


higher


molecular


weight


polyacetylene


partially


soluble


CDC3,


actua


average


molecular


weight


entire


sample


could


higher


than


that


calculated from


NMR


spectra.


spectrometry


showed


that


highest


detectable


length


repeat


units,


and


permeation chromatography


(GPC)


vs. polybutadiene standards shows


average


produced


repeat


this


step,


units.


Only


condensation


polyacetylene
, equilibrium


oligomers


were


polymerization


because


methyl


terminated


polyacetylenes


have


high


melting


points18


(4-ene,


5-ene


, mp


150 oC)


and solidify at low


degrees


polymerization.


manner


terminal


olefins


polyacetylene


oligomers


restricted


from


further


metathesis


condensation.


The


spectra of


2,4-hexadiene and the soluble portion of its


polymers


shown


Figure


3.6.


According


work


Nayler162 and


Spangler,163


unsubstituted


methyl-terminated


polyacetylene


oligomer


containing


more


than


three


double


bonds


showed three


main


absorbances.


Compared with


spectra


individual


ene


methyl


units)


terminated


Nayler's


polyacetylene


paper,


oligomers


multiple


(3-ene


absorption


polyacetylenes


here


could


attributed


different


polyacetylen
terminated


chain


lengths.


polyacetylene


from


The
bulk


highest absorption


polymerization


of the


was


methyl-


423







349


which


could


assigned


repeat


units.


The


chain


length


exhibited


spectrum


was


consistent with


that from


the NMR spectrum for the same sample.


---- 2,4-Hexadiene
-- Polyacetylene from bulk
polymerization of 2,4-
hexadiene


I'
iF'
'I
I'
I'
I'
I'
I
I'
'-.4


300 400


Wavelength


(nm)


Figure 3.6.


The UV


spectra of


4-hexadiene and its bulk


polymerization


polyacetylene.


Solution


ADMET


Polymerization


versus


Bulk ADMET Polymerization


There are


techniques


ADMET


polymerization


increase


the molecular weight of a polymer product.


One


technique is to raise


reaction


temperature,


where


VISCOS


polymer


decreases


with


increase


temperature.


The


molecular weight,


therefore,


increases


with


continuing


condensation


terminal


olefin


and


remove


sinaI


molecules


fro m


reaction


system


. This


method was


1


mited


.I I


ADMET


oolvmerization


the deactivation


.






second


technique


increase


molecular


weight


polymer
molecular


use


weight


solution


polymer


polymerization


method,


increases


high


where


molecular


weight
of the


polymers


precipitate


polymer reaches


from


solution


a point where


terminal


molecular


olefin


weight


metathesis


condensation


is stopped


ADMET


polymerization


2,4-hexadiene


molecular


solution


weight
which


increase


polyacetylene


allowed


solution


oligomers


were


polyacetylene


polymerization.


When


soluble


molecular


toluene


weight


2,4-hexadiene


was


dissolved


polyacetylene


toluene,


oligomers


followed


remained


addition


soluble


catalyst,


approximately


before precipitating.


manner


, polyacetylenes


with an


average


10-15


double


bond


units


were


prepared


as determined


NMR


spectroscopy.


spectrometry


(MS)


showed


that


highest


detectable


length


solution


polymerization


polyacetylenes


from


2,4-hexadiene


repeat


units,


and


permeation


chromatography


(GPC)


versus


polybutadiene


standards


showed


average
product


repeat


showed


units.


higher


The


molecular


solution


(1.0


weight


polymerization


than


bulk


polymerization


product.


The


spectra


(Figure


3.7)


confirmed


that


solution


polymerization
polymerization


absorption


polyacetylenes


polyacetylenes.


solution


had


onger


lengths


slightly


polymerization


longer


than


bulk


wavelength


polyacetylenes


was










S
I.
mm
II
II


II

-/ js 'I


2,4-Hexadiene
Polyacetylene from bulk polymeri-
zation of 2,4-hexadiene
Polyacetylene from solution polymeri-
zation of 2,4-hexadiene


300 400 500


Wavelength


(nm)


Figure 3


spectra of


4-hexadiene and its bulk and solution


ADMET


polyacetylenes.


ADMET Polymerization of an


Internal Conjugated Triene,


2,4,6-Octatriene


Bulk


polymerization


2,4,6-octatriene


was


conducted


room


temperature


using


Lewis


acid-free


molybdenum catalyst


(Figure

obtained


3.8).


Methyl-terminated


polyacetylene


oligomers


were


Cat.


CH3{-4~CH3


Figure 3.8.


ADMET


polymerization


4,6-octatriene.