Acyclic diene metathesis (ADMET) polymerization

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Acyclic diene metathesis (ADMET) polymerization the polymerization of carbonyl-containing dienes
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Patton, Jasson Todd, 1964-
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Thesis (Ph. D.)--University of Florida, 1992.
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Includes bibliographical references (leaves 82-87).
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by Jasson Todd Patton.
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Vita.

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ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE POLYMERIZATION OF CARBONYL-CONTAINING DIENES













By

JASSON TODD PATRON


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

1992


UNIVESITY OF FLORIDA LIERAIES





















Press On
Nothing in the world can take the place of
persistence. Talent will not; nothing is more
common than unsuccessful men with talent.
Genius will not; unrewarded genius is almost
a proverb. Education alone will not; the
world is full of educated derelicts. Persistence
and determination alone are omnipotent.


Calvin Coolidge












ACKNOWLEDGMENTS


The original research presented by this dissertation would not
have been completed without the experience, wisdom, and
knowledge of the following scientists: L. Blosch, M. Forbes, S.
Gamble, J. Konzelman, J. Linert, K. Novak, J. Portmess, D. Smith,
D. Tau, and F. Zuluaga. Sincere thanks is extended to each of them.
In addition, I thank the members of my graduate committee: Dr.
J. Boncella, Dr. E. Enholm, Dr. A. Green, and Dr. K. Schanze.
Sincere thanks go to my wife Carolina Lopez, to whom this
document is dedicated, for her unfailing support and
encouragement. Carolina is responsible for reminding me that the
pursuit of a career is only one of life's worthwhile endeavors.
Finally, I thank my thesis advisor, Dr. K. Wagener, who taught
me as much about keeping an optimistic outlook on life as he did
about chemistry.












TABLE OF CONTENTS


Page
ACKNOW LEDGMENTS..................................................................................... iii
ABSTRACT.................................................................................................. iv
CHAPTERS


1 INTRODUCTION..................................... ............................................ 1


Mechanism of the Olefin Metathesis Reaction............................... 3

Classical Catalyst Systems used in Metathesis
Polymerizations................................................ .............................. 8

Ring Opening Metathesis Polymerization (ROMP)
and the Synthesis of Well Defined Catalyst Systems........... 1 0

Acyclic Diene Metathesis (ADMET) Polymerization....................1 4


2 ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE SYNTHESIS OF UNSATURATED POLYESTERS......................... 2 2


ADMET Synthesis of Unsaturated Polyesters and
the Negative Neighboring Group Effect................................... 25

Unsaturated Polyester Characterization and
M olecular W eight Analysis............................................ ........... 29

Thermal Analysis of the Unsaturated Polyesters..................... 3 1

Kinetic Advantage of the Molybdenum Based
Catalyst Versus that of .Tungsten......................................... 34









3 ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE SYNTHESIS OF UNSATURATED POLYCARBONATES............ 36


ADMET Synthesis of Unsaturated Polycarbonates
and the Negative Neighboring Group Effect.......................... 38

Unsaturated Polycarbonate Characterization and
Molecular Weight Analysis......................................................... 40

Thermal Analysis of the Unsaturated Polycarbonates............. 43


4 ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE SYNTHESIS OF UNSATURATED POLYKETONES..................... 47


Synthesis of Unsaturated Polyketones......................... ........... 48

Unsaturated Polyketone Characterization and
Molecular Weight Analysis......................................................... 50

ADMET Cyclization of Ketone Containing Dienes....................... 51


Sum m ary............................................................................................... 5 8


5 EXPERIM ENTAL..................................................................................... 59


General Information........................................................................ 59

Synthesis of 1,4 Benzene dicarboxylic-
bis (1-hexenyl) ester.............................. ...................................... 60

Synthesis of 1,4 Benzene dicarboxylic bis (1-pentenyl)-
ester................................................................................... ............. 6 1

Synthesis of 1,4 Benzene dicarboxylic bis (1-butenyl)-
ester.................................................................................................. 6 2

Synthesis of 1,4 Benzene dicarboxylic bis (1-propenyl)-
ester.................................. ............................................................... 6 2
v








Synthesis of 1-Hexene-l-pentenoate............................................ 63
Synthesis of 1-Hexene-l-butenoate............................ ........... 63
Synthesis of Poly (oxy-5-decene-oxyteraphthaloyl).............. 64
Room Temperature Synthesis of Poly (oxy-5-decene-
oxyteraphthaloyl).................................................... ........................... 65
Synthesis of Poly (oxy-4-octene-oxyteraphthaloyl)................. 65
Synthesis of Poly (oxy-3-hexene-oxyteraphthaloyl).............. 66
Synthesis of Poly [oxy-(3-octene) ester]...................................... 66
Attempted Polymerization of 1-Hexene-l-propenoate.......... 67
Copolymerization of 1,4 Benzene dicarboxylic bis-
(1-pentenyl) ester and 1,9 Decadiene................................... 67
Synthesis of Benzene carboxylic (1-propenyl) ester............... 68
Synthesis of Bis (1-hexenyl) carbonate................................... 68
Synthesis of Bis (1-pentenyl) carbonate................................... 69
Synthesis of Bis (1-butenyl) carbonate................................... 69
Synthesis of Bis (1-propenyl) carbonate................................... 70
Synthesis of 1,4 Phenylene-iso-propylidene-1,4-
phenylene-bis(1-butenyl) carbonate........................................ 70
Synthesis of Poly (5-decene) carbonate.....................................
Synthesis of Poly (4-octene) carbonate..................................... 7 2
Synthesis of Poly (3-hexene) carbonate........................................ 72
Attempted Polymerization of Bis (1-propenyl)-
carbonate.................................................................................... ..... 7 2
Synthesis of Poly (oxycarbonyloxy-l,4-phenylene-iso-
propylidene-1,4-phenylene-oxycarbonyloxy-
3-hexene)........................................................................................ 7 3
Dilute Solution Polymerization of Poly (oxycarbonyloxy-
1,4-phenylene-iso-propylidene-1,4-phenylene-
oxycarbonyloxy-3-hexene)........................................ ............ 74








Synthesis of Poly[1-oxo-2, 2, 11, ll-tetramethyl-6-
undecenylene ................................................................................... 7 4
Synthesis of Poly[(7-oxo-6, 6, 8, 8-tetramethyl-1-
undecenylene)-co- -octenylene]........................................... 74
Synthesis of Poly[(1-hexenylene-1, 3-dimethyl-1, 3-
cyclododecylene-2-oxo-3-propylene)-co-1-
octenylene]......................................................... ............................. 7 5
Synthesis of Poly[(1-propylene-1, 3-cyclododecylene-
2-oxo-3-propylene)-co- -octenylene]................................... 76
Synthesis of Poly[(1-propylene-trans- ,3-dimethyl-
1,3-cyclododecylene-2-oxo-3-methylene)-co-
1-octenylene]................................................................ .................. 7 6
Synthesis of 4,4,6,6-Tetramethyl-1,8-nonadiene-
5-one..................................................................................................... 7 7
Synthesis of 2,2,7,7-Tetramethyl-4-cycloheptene-
1-one................................................................................................... 7 8
Synthesis of 1,11-Dimethyl-bicyclo-[9.4.1]-13-
hexadecene-16-one........................................................................... 7 8
Synthesis of 1-(2,2-Dimethyl-propane-l-one)-
1-methyl-3-cyclopentene........................................................... 7 9
Synthesis of 1-(2-Methyl-2-phenyl-propane-l-one)-
1-methyl-3-cyclopentene............................................................ 7 9
Synthesis of 1,1-Dimethylester-3-cyclopentene............. ...... 80
Synthesis of 1-(2, 2-Dimethyl-propane-l-one)-
1-methyl-3-cyclohexene.............................................................. 80
Synthesis of 1-(2,2-Dimethyl-propane-l-one)-
1-m ethyl-4-cycloheptane............................................................... 8 1


REFEREN CES..................................................................................................... 8 2
BIOGRAPHICAL SKETCH............................................ .................. 8 8












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



ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE POLYMERIZATION OF CARBONYL-CONTAINING DIENES


By


Jasson Todd Patton


DECEMBER 1992



Chairman: Dr. K. B. Wagener
Major Department: Chemistry


Various monomers containing the carbonyl group have been
investigated in order to study the acyclic diene metathesis (ADMET)
polymerization of highly polar functionalities. The carbonyl
containing dienes possessed the ester, carbonate, and ketone
groups. These monomers were also used to study structure control
in the repeat unit and structure reactivity relationships of the
monomer.


viii








New unsaturated polyester, polycarbonate, and polyketone
structures have been synthesized via the acyclic diene metathesis
(ADMET) polymerization. The polymerizations were performed
using the catalyst Mo(CHCMe2R)(N-2,6-C6H3-i-Pr2)[OCCH3(CF3)212
(R = Me, Ph) which was found to be much faster in the metathesis
of some terminal olefins than its tungsten counterpart.
No metathesis activity is observed for ester or carbonate
containing dienes when only one methylene spacer is present
between the functionality and the olefin due to a negative
neighboring group effect. This negative neighboring group effect
involves either the coordination of the carbonyl oxygen to the metal
center or simply the polarization of the double bond such that the
intermediates of the metathesis process are not favored.
Some substituted ketone containing dienes were found to
undergo cyclization rather than linear polymerization to yield five,
six, or seven-membered rings. The cyclizations are due to a
"Thorpe-Ingold" effect forcing the reactants into a horseshoe
conformation conductive to cyclization.














CHAPTER 1


INTRODUCTION


Successful polymer chemistry is based on predictable reactions
that join one molecule to another. Two of the most challenging
aspects of polymer synthesis relate to structure control in the
repeat unit and to the structure reactivity relationships of the
monomers themselves. Both of these challenges are dealt with in
this dissertation, specifically with regard to the preparation, via
acyclic diene metathesis (ADMET) polymerization, of a new class of
unsaturated polymers containing the carbonyl functionality.
Olefin metathesis describes the interchange of carbon atoms
between a pair of double bonds. Metathesis can be demonstrated
with three general types of reactions (Figure 1.1).1 The term olefinn
metathesis" was first coined by Calderon in 1967, and the first
publications describing olefin metathesis reactions involved the
ring opening polymerization of norbornene (Figure 1.1.2) and the
exchange reaction of propene (Figure 1.1.1).2,3 These publications
were preceded by patent disclosures as early as 1957.1,4 Early
work in the field of olefin metathesis has led to more than 35 years
of scientific research in the field as well as several very important







1.1.1) Exchange Reactions


CH3CH=CH2
+ Catalyst
CH3CH=CH2
1.1.2) Polymerization Reactions


SCatalyst


1.1.3) Degradation Reactions


Catalyst


CH3CH=CHCH3

CHCH2
CH2=CH2


. 1+


Figure 1.1. Three types of olefin metathesis reactions.


commercial applications. Particularly important has been the work
in determining the mechanism responsible for metathesis
chemistry, research which is described in the following section.


Mechanism of the Olefin Metathesis Reaction


A pairwise mechanism was originally proposed as the pathway
for olefin metathesis where the chemistry was thought to occur
when two double bonds approached one another in the vicinity of a
transition metal catalyst site (Figure 1.2.1).1 The transition metal
orbitals were believed to overlap with the olefin double bonds to
allow exchange to occur via a weakly held cyclobutane type


'-*ND

J







complex. While this mechanism predicted most products
successfully, it was eventually abandoned in favor of the metal
carbene mechanism proposed in 1970 by Chauvin (Figure 1.2.2).5.6
The evidence supporting the latter mechanism is vast, with
perhaps the strongest support coming from the study of cross-
metathesis reactions as well as the reactions of isolable metal
carbenes with olefins which allowed the direct spectroscopic
observation of metal carbene complexes and metallacyclobutane
complexes.1
The evidence in favor of the metal carbene mechanism from
cross-metathesis reactions arises from the analysis of the statistical
ratio of the of the reaction products possible from the two
mechanisms. A metathesis reaction between cyclopentene and the
unsymmetrical olefin, pent-2-ene, would lead initially to the
formation of 2,7-decadiene by the pairwise mechanism. However,
when the reaction was performed using WOCl4/Bu4Sn or WOC14/



CHRI CHR3 RiHC- -CHR3' RiHC=CHR3
1.2.1) I [M II i -a- a
CHR2 CHR4 R2HC----CHR4 R2HC= CHR4


CHRI CHR2 R1HC- CHR2 RHC=CHR2

[M] CHR3 [M]-CHR3 [M]=CHR3

Figure 1.2. Proposed mechanisms for olefin metathesis where [M]
represents a transition metal catalyst.








Et2AICl as catalysts the products found were 2,7-nonadiene, 2,7-
decadiene, and 3,8-undecadiene in the statistical ratio of 1:2:1
(Figure 1.3).5 It was this observation which led to the proposal of
the metal carbene mechanism. The formation of the ratio of
products is explained in terms of the sequence of reactions shown
in Figure 1.4. Similar results were obtained with cyclooctene,
cycloocta-1,5-diene, cyclododeca-1,5,9-triene in place of
cyclopentene.
These results alone, however, did not disprove the pairwise
mechanism. If one of the olefinic bonds remains attached to the
catalyst site after the reaction, until another acyclic olefin becomes





Pairwise
Metal Carbene M eanise
MechanismMechanism



1
+

2

+





Figure 1.3. Expected products and ratios of the metal carbene and
the pairwise mechanisms.








attached at the vacant site, the formation of 2,7-nonadiene and
3,8-undecadiene can be accounted for as a result of a very rapid
second reaction. This explanation was referred to as the sticky
olefin mechanism.1
A more decisive experiment was that of a double cross
metathesis reaction when cyclooctene was reacted with a mixture
of but-2-ene and oct-4-ene (Figure 1.5).7 In the case of each of the
proposed mechanisms the predicted values of (n2/nl)(n2/n3) are
4.0 for the metal carbene mechanism, 0.0 for the simple pairwise
mechanism, and 2.7 for the sticky pairwise mechanism. The actual
values obtained for (n2/nl)(n2/n3) were 4.05 for cis reactants and
4.1 for trans reactants. This experiment shows that both types of
pairwise mechanisms must be rejected in favor of the metal
carbene mechanism.
The evidence in favor of the metal carbene mechanism from the
reactions of isolable metal carbenes with olefins is vast and rapidly
growing today due to the synthesis of well defined catalyst
systems. The first cases of characterizing initiating and propagating
metal carbene species by NMR were reported in 1980.8,9 The first
reactions involved Me3CCH=WC 2(0)(PEt3)2 activated by AICI3
which induced the metathesis of but-1-ene and of pent-1-ene. In
the case of but-1-ene the species EtCH=WCI2(0)(PEt3)2 and
CH2=WCl2(0)(PEt3)2 are both detectable by 1H NMR. The carbene
protons appear at 12.03 ppm for the reactant, 12.1 ppm for
EtCH=WCI2(0)(PEt3)2, and 12.34 and 11.47 ppm for
CH2=WC12(0)(PEt3)2. The nonequivelence of the protons in
CH2=WCl2(0)(PEt3)2 and the fact that there is only one chemical







[M= CHCH3
+


+ [M]


[M== CHCH2CH3
+


[M== CHCH3


S[MI== CHCH2CH3


[M]= CHCH3


[M==CHCH2CH3


+--


[M]==CHCH3


Figure 1.4.


[M ==CHCH2CH3
Reaction sequence demonstrating the formation of
the product ratios where [W] is a tungsten based
metathesis catalyst.


0 +


+ 0--









0+


+


3

Figure 1.5. Metathesis reaction demonstrating that both types
of pairwise mechanisms must be rejected.

shift for EtCH=WC12(0)(PEt3)2 demonstrates that the carbene ligand
has a fixed orientation with respect to the other ligands. For the
reaction with pent-2-ene the propagating carbenes,
EtCH=WCl2(0)(PEt3)2 and MeCH=WCl2(0)(PEt3)2 are both present in
comparable amounts.9 There are many examples since these
experiments in which metal carbenes and metallacycles have been
isolated and extensively characterized.


Classical Catalyst Systems used in Metathesis Polymerizations


Classical
the olefin
components,
complex and


catalyst systems that have been extensively studied in
metathesis reaction commonly employ multiple
which are generally based on a transition metal
an accompanying co-catalyst that serves as a Lewis







acid to activate the transition metal catalyst. In these classical
systems, it is assumed that the acting catalyst is a metal carbene;
however, the nature and the origin of these metal carbenes often
are not known or understood. In addition, classical metal catalyzed
polymerizations are often plagued by a variety of side reactions
which are not easily monitored.
Many classical catalyst systems have been studied in an
attempt to elucidate the formation and nature of the active species.
The WC16/LiCH2SiMe3 catalyst system produces Me3SiCI suggesting
that CH2=WCl4is the reactive species (Figure 1.6).10 The
WCl6/Me4Sn and WCl6/Me2Zn systems both generate CH4 making it
reasonable to postulate the formation of CH2=WCl4 in these cases as
well; however, the true nature of these catalyst systems have yet
to be proven.11,12
The first evidence that the transition metal exists in a very high
oxidation state appeared when isolable complexes of the type
W(CH-t-Bu)(O)L2Cl2 (L=trialkylphosphine) were found to promote a
metathesis reaction in the presence of AICl3 to yield
W(CHR')(O)L2Cl2 complexes.8 Soon after, complexes of the type
W(CH-t-Bu)(OR)2X2, were shown to be extraordinarily active
toward olefin metathesis in the presence of AIX3. The four co-
ordinate cationic species of the form, [W(CHR')(OR)yX3-y]+, are be-
lieved to be the most active of components of these systems.8,13-17

WC16 + LiCH2SiMe3 -- Me3SiCH2WC1 Me3SiCI + CH2=WC4
observed postulated

Figure 1.6. Typical classical metathesis catalyst in which the
active catalyst system is poorly defined.








The most important catalyst systems are based on the fourteen
transition elements shown in Table 1.1.1 Over the last three
decades vast numbers of catalyst systems have been explored for
their proficiency in the olefin metathesis reaction. The most
successful catalyst systems, by far, have been based on the
transition metals, tungsten and molybdenum. The primary
limitation of these catalysts is their inability to be prepared
systematically and their reactivity controlled by rational means.
This limitation has been a particularly frustrating problem in the
search for catalyst systems compatible with functional groups and
eventually led to the synthesis of well defined catalyst systems.


Table 1.1. Transition elements commonly used as catalysts.


Group IVA Group VA Group VIA Group VIIA Group VIII
Ti V Cr
Zr Nb Mo Ru Rh
Hf Ta W Re Os Ir



Ring Opening Metathesis Polymerization (ROMP) and the Synthesis
of Well-Defined Catalyst Systems


In recent years research in the area of ROMP has led to the
development of very active and well-defined metathesis catalyst
systems. The belief was that a highly active four coordinate,
neutral olefin metathesis catalyst would alleviate the potential for
complications that can occur in the presence of highly active








cationic catalyst systems, and the first of these well defined
catalyst systems was developed by Schrock (Figure 1.7).13,18 These
catalyst systems are well defined in that the initial metal complex
is already a metal carbene which is not the case with most classical
olefin metathesis catalysts. These well defined systems have led to
a far greater understanding of the olefin metathesis reaction than
was previously attainable since it allows substituted and
unsubstituted metallacyclobutanes to be isolated and
characterized.13,18 These well defined catalyst systems have also
allowed various mechanistic as well as kinetic studies to be
performed which were not feasible for classical catalysts.13
The tungsten based metal complex, W(CH-t-Bu)(N-2,6-C6H3-i-
Pr2)(OR)2, synthesized by Schrock, was the first Lewis acid-free
catalyst system to be studied.18 In addition to the factors
mentioned above, this complex showed that catalysts can be
prepared systematically and their reactivity controlled by rational
means. An example can be seen in the case where the complex
W(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(OR)2 was prepared and the
metathesis activity controlled through the choice of the alkoxide
ligand.13 While several model studies were done, the one most




N
II /H
W=C
/ >.
[RO]2
Figure 1.7. Lewis acid-free catalyst developed for ROMP.







[w]
+ CH2=CH2



N
[W]= II /H
W= C
/ y.
[RO]2


Figure 1.8. Dependence of metathesis rates on alkoxide.


relevant to this research was the metathesis of 1-pentene to give
neohexene. In the case where R=C(CH)3, the reaction proceeded
slowly reaching 70% conversion after eight hours. In neither case
are more than a few turnovers to ethylene and 4-octenes observed
in several hours (Figure 1.8). When R=C(CH3)2CF3 was employed as
the alkoxide, the reaction was faster but as in the previous case
only low conversions to ethylene and 4-octenes were observed.
However, in the case where R=CCH3(CF3)2, the reaction was very
rapid and reached 75% conversion after only ten minutes to give
W(CHPr)(NAr)[OCCH3(CF3)212, the beta-substitited tungstacycle
W(CH2CHPrCH2)(NAr)[OCCH3(CF3)2]2, and the unsubstituted
metallacycle W(CH2CH2CH2)(NAr)[OCCH3(CF3)2]2. Experiments have
shown that the reason for the differences in reactivity lies in the
fact that the stability of the intermediate metallacycles when
R=CCH3(CF3)2 is far greater than in the other two cases where the
alkoxide ligands are less electron withdrawing. In the final case
where R=C(CF3)2(CF2CF2CF3) again only low conversions were
observed despite immediate catalyst reaction.







Two possible reasons for this last observation are that the beta-
propyl metallacycle may be relatively stable toward loss of olefin
(Figure 1.9.1), or, for steric reasons it may be the only
metallacycle that forms (Figure 1.9.2). This study of alkoxide
ligands showed that catalyst structures can be systematically
produced and the reactivity controlled by the choice of the alkoxide
ligand. The final results of this study clearly show that the most
active olefin metathesis catalyst of this series has R=CCH3(CF3)2 as
the alkoxide.13
The nature of the metal center also affects catalyst reactivity,
and the purpose of investigating catalyst systems based on various
metal centers has been to find active systems compatible with
functional groups.19,20 For example, when W(CH-t-Bu)(N-2,6-C6H3-
i-Pr2)(OCCH3(CF3)2)2 was reacted with ethyl acetate or cis-methyl-
9-octadecenoate the catalyst lifetime was limited by a Wittig type
reaction (Figure 1.10). This chemistry has been observed in
catalyst systems based on tantalum, titanium, and zirconium as
well as tungsten.21 The molybdenum analogue of catalyst W(CH-t-


1.9.1) [W]=CH2 + -" tw



1.9.2) [W]=CH2 + .[W




Figure 1.9. Possible reactions of tungstacyclobutane complexes
when [W]=W(N-2,6-C6H3-i-Pr2)(OCCH3(CF3)2)2 and
R-C(CF3)2(CF2CF2CF3).







O O
II II
[W]=CHR + R'COMe [W] + RHC=CR'(OMe)

Figure 1.10. Wittig-type chemistry of a tungsten-based catalyst
where R=t-butyl and [W]=W(N-2,6-C6H3-
i-Pr2)(OR)2.


Bu)(N-2,6-C6H3-i-Pr2)(OR)2 was synthesized for the reason that the
metal-carbon bond in Mo(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(OR)2 is not as
strongly polarized as in the tungsten analogue.19 This lack of
polarization means that the molybdenum based catalyst might not
react as readily with highly polar functionalities such as the ester
group.
The experimental evidence that the molybdenum based catalyst
is more tolerant to the carbonyl functionality than the tungsten
based catalyst is considerable.19-27 Mo(CH-t-Bu)(N-2,6-C6H3-i-
Pr2)(OC(CH)3)2 did not react with ethyl acetate or with N, N-
dimethylformamide even over a period of several days meaning
that the catalyst was stable to some highly polar functionalities.20
Mo(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(OR)2 was found to react rapidly in a
Wittig fashion with benzaldehyde when R=C(CH)3 and R=CCH3(CF3)2.
The same catalysts also reacted rapidly with acetone; however, the
products could not be identified.
Similar results were obtained when an actual polymerization
was carried out using the different metal based catalysts. W(CH-t-
Bu)(N-2,6-C6H3-i-Pr2)(OC(CH)3)2 was found to polymerize endo,
endo-5,6-dicarbomethoxynorbornene, but the catalyst was rapidly








r"2 [Mo] / =CH(t-Bu)
[Mo] CH(t-Bu) + X [Mo CH(t[
C2COMMe COMe

Figure 1.11. Living polymerization of endo, endo-5, 6-
dicarbomethoxynorbornene.


destroyed and the molecular weight therefore cannot be controlled.
However, when endo, endo-5,6-dicarbomethoxynorbornene is
reacted with Mo(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(OC(CH)3)2, a polymer
is produced that has a low polydispersity, characteristic of a living
polymerization catalyst system (Figure 1.11).19 This initiated a vast
research effort to polymerize many functionalized norbornenes in
addition to the ester functionality.22-24,26-27


Acyclic Diene Metathesis (ADMET) Polymerization


A second approach to olefin metathesis polymerization via
acyclic diene metathesis (ADMET) chemistry was conceived many
years ago but was not realized until 1987.28 An ADMET
polymerization involves an olefin exchange reaction (Figure 1.1.1)
where the monomer is a diene (Figure 1.12). The ADMET
polymerization is a step condensation polymerization driven by the
removal of the condensate, and since the polymerization involves



X CatalystL X + CH2=CH2


Figure 1.12. Acyclic Diene Metathesis (ADMET) polymerization.







an equilibrium process, the polymerization is reversible.29 Early
experiments attempting to polymerize 1,9-decadiene and 1,5-hexa-
diene to polyoctenomer and polybutadiene, respectively, failed.28
These experiments employed classical catalyst systems such as
WC16/EtAlCl2, and while metathesis products were observed, a
large percentage of intractable material resulted.
The intractable material was shown to be the result of a
competing vinyl addition reaction resulting from the formation of a
cation due to the presence of the Lewis-acid. The vinyl addition
reaction was shown to be the side reaction most clearly in a model
study using styrene (Figure 1.13). In the case of styrene, if
metathesis occurs then the resulting product is stilbene; however,

R4

R2

R2
WCl6/EtAICl R3


RF
R4 R R



R, R + R
R3 R2 R4

R3

Figure 1.13. ADMET model study with styrene and a classical
catalyst system (R1, R2, and R3 are either F, H, Br,
or CH3 or combinations thereof. R4 is either H
or CH3.).








if vinyl addition occurs then the product is polystyrene. As
illustrated in Figure 1.13, the only observed product is
polystyrene.28
The development of the Lewis acid-free catalyst systems
(Figure 1.7) discussed previously offered the possibility of using a
catalyst system where the cationic center is not formed in the
activation of the catalyst.18 Without the formation of the cationic
center the vinyl addition reaction should not be initiated and the
only product observed should be stilbene if any product forms at
all. This was, in fact, observed to be the case (Figure 1.14). This
result initiated the investigation of ADMET polymerization as a
viable route for the synthesis of high molecular weight unsaturated
polymers.30-34


R4

R, z9
II .H

R2 W =C




R, x RRI R4

R R R4
R2/ R,?/ +

R3 R2 R4
R3

Figure 1.14. ADMET model study with styrene and a Lewis acid-
free catalyst system (RI, R2, and R3 are either F, H,
Br, or CH3 or combinations thereof. R4 is either H or
CH3.).










Reactant


1.15.1)

1.15.2)

1.15.3)

1.15.4)

1.15.5)

1.15.6)

1.15.7)

1.15.8)

1.15.9)
1.15.10)

1.15.11)

1.15.12)

1.15.13)

1.15.14)


1.15.15)


1.15.16)


Iu
C"JI..


Figure 1.15.


ADMET polymerizations and model studies involving
hydrocarbon reactants.


Product


No Reaction





No Reaction


SNo Reaction

No Reaction
SNo Reaction

No Reaction


~-~y~
i*`


II`








The first ADMET polymerization carried out produced
polyoctenomer from 1,9-decadiene (Figure 1.15.1); the polymer
was perfectly linear and 90% trans in its stereochemistry. These
characteristics were found to be the general case for ADMET
polymerizations. This polymerization was followed by the
polymerization of 1,5-hexadiene to poly-1,4-butadiene (Figure
1.15.2). Copolymerizations were then carried out using 1,5-
hexadiene and 1,9-decadiene forming perfectly random, linear
poly(butadiene-co-octenomer) copolymers.35 .The successful
polymerization of the perfectly linear acyclic dienes led to a
hydrocarbon monomer structure reactivity study (Figure 1.15.3-
1.15.16).36 Copolymerizations were also carried out between 1,9-
decadiene and 1,4-dipropylenebenzene (Figure 1.15.5).37 All of the
reactions involving the ADMET reaction of simple alkyl olefins are
shown in Figure 1.15 for completeness.
The proposed mechanism for ADMET polymerization is similar
to that of ROMP since the catalytic cycle involves the formation and
decomposition of various metallacycles. It differs, however, from
that of ROMP since in the course of the reaction the active catalyst
actually breaks free from the polymer chain (Figure 1.16).34 While
the proposed mechanism is speculative in nature, it is rational
since intermediates such as those shown in Figure 1.16 have all
been observed in similar systems. The polymerization cannot be
considered living since the reaction has been shown to follow the
Caruther's relationship for non-living step condensation polymers.38
The experiments discussed above clearly show that unhindered
hydrocarbon monomers can b'e polymerized successfully. It was








+ LMCR2

'X1 + LnM=CR2 LnM
R R


C2H4



XA

LnM


R2C=CH2

X X
LnM=--C or
H polymer


LnM X

LnMX-


X LnM--C X X
H

Figure 1.16. Proposed mechanism for the ADMET polymerization of
1,9-decadiene.


1991, however, before the ADMET polymerization of olefins
containing heteroatoms was successfully demonstrated. The first of
these polar olefins to be successfully polymerized were those
containing the ether functionality (Figure 1.17).39,40 These
polymerizations performed by Brzezinska demonstrated the ability


0 C-atayst O_


+ CH2=CH2


Figure 1.17. ADMET polymerization of ether containing olefins.








Reactant


CH3 CH3
si
1.18.1) S

CH3 CH3
\Si/
1.18.2) i N S

c43 >H3

CH3 CH3 CH3 CH3
1.18.3) =/

CH3 CH3
1.18.4) +

CH3 CH3 CH3 CH3
1.18.5) 1 .S % I/


CH3 CH3 CH3 CH3
1.18.6) S, O,


CH3 CH3CH3 CH3 CH3 CH3
'I / .I .I
1.18.7) Si S O ,,S i S I

CH3 CH3CH3 CH3
1.18.8) Si Si


CH3 CH3

(i

CH3 CH3


c63>H3 x
CH3 CH3 CH3 CH3
Si si

CH3 CH3




No Reaction


CH3 CH3
\ 0 /
CH3-SI ISiiCH3


CH3 CH CH3 CH3 CH3 CH3
-[ % 0 0 S i


CH3 CH3 CH CH
rl .j .I/
-f '^O3^^ ^ ^


Figure 1.18. ADMET synthesis of poly[carbo(dimethyl)silanes] and
poly(carbosiloxanes).


to polymerize monomers with polar functionalities, monomers

which were previously believed to coordinate to the unsaturated

metal center and therefore block any reactivity. This series of


Product








polymers was also the first reported example of unsaturated
polyethers.
Soon after the ether group was shown to be tolerant toward the
metathesis reaction, the silane and siloxane functionalities were
introduced by Smith as a polymerizable functionalities (Figure
1.18).41-43 Figure 1.18.1-1.18.4 demonstrates the ability to
synthesize polycarbosilanes, while Figure 1.18.5-1.18.8
demonstrates the ability to synthesis unsaturated polysiloxanes.
Again, all reactions are shown in this figure for completeness.
Establishing that monomers other than simple alkyl olefins can
be successfully polymerized demonstrated that unsaturated
polymers with highly polar functionalities might be synthesized.
The polymerization of monomers containing the highly polar
carbonyl group forms the basis of this dissertation (Figure 1.19).
Polymers containing the ester, carbonate, and ketone containing
functionalities are described in the following chapters, where
structure/reactivity relationships are delineated in each case. The
chemistry is unprecedented and has led to completely new polymer
structures.


R-XR tt R-X-R + CH2=CH2


0 0 0
X = -C-, -, -OCO- R = -(CH2)-x


Figure 1.19. ADMET polymerization of carbonyl containing
monomers.















CHAPTER 2


ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE SYNTHESIS OF UNSATURATED POLYESTERS


Various monomers containing the carbonyl group have been

investigated in order to study the ADMET polymerization of highly

polar functionalities. The first carbonyl containing functionality

studied was the ester group where these ester containing dienes

were condensed to yield unsaturated polyesters. Ketone and the

carbonate functionalities are presented in subsequent chapters.
Conventional methods of preparing unsaturated polyesters

involve the polycondensation reaction at elevated temperature

between glycols and dibasic acids, esters, or anhydrides (Figure

2.1).38,44 The useful range of number average molecular weights
for these polymers is generally moderate (15,000 to 20,000),

allowing for easy processibility via molding or coating. Curing of

the olefin present in the repeat units is then performed via thermal

0
0 01
II I
H-O-f-CHg)n-O-H + O HO--fCH- rOCCH = HCCO-H + XH2

0


Figure 2.1. Conventional synthesis of unsaturated polyesters.
22








or irradiation methods. These conventional methods can result in a

significant loss of unsaturation and branching during the

polyesterification step. Thus, ADMET polymerization may offer a

better route to unsaturated polyesters.

The metathesis of carbonyl containing compounds has received

attention in the past.l Until the development of Lewis acid free

metathesis catalyst systems, however, the metathesis of

unsaturated compounds containing the carbonyl functionality had

been unsuccessful due to the rapid poisoning of the catalyst system.

Only low conversions were observed, and thus, highly reactive

classical homogeneous metathesis catalyst systems such as WCI6-

SnMe4 and WOCl4-SnMe4 have seen only limited success in the

metathesis of unsaturated esters. Heterogeneous catalyst systems

based on Re207/A1203-SnMe4 also have been used in the

attempted metathesis of unsaturated esters; however, as in the

case for previous homogeneous catalyst systems, conversions are

less than the necessary >99% required for successful step

polymerization chemistry.1,45


N
I //H
M ==C
/ 2
[CH3(CF3)2CO] 2 \
R


Figure 2.2. SchroGk's olefin metathesis catalyst.


Catalyst M R

la Mo Ph
lb Mo CH3
2a W Ph
2b W CH3








AT( \-0=r Ct.N + CH2=CH2


Figure 2.3. Aromatic unsaturated polyesters synthesised via the
ADMET polymerization.


The molybdenum analog of Schrock's catalyst (Figure 2.2) has
been described to be more tolerant of the carbonyl functionality as
demonstrated in its application in the ring opening metathesis
polymerization of functionalized norbornenes.13,18-23 This
chapter reports the first successful acyclic diene metathesis
(ADMET) polymerization of an ester-containing monomer using this
molybdenum based catalyst and demonstrates the successful
polymerization of monomers containing a high degree of polar
functionality, leading to unsaturated polymers possessing a high
degree of crystallinity (Figure 2.3). Simple alkyl monomers were
also used to define the synthesis rules of the ADMET polymerization
of monomers containing the ester functionality (Figure 2.4).

So
-Q)ft_ + CH2=CH2


Figure 2.4. Simple unsaturated alkyl polyesters synthesized via
ADMET polymerization.

ADMET Synthesis of Unsaturated Polyesters and the Negative
Neighboring Group Effect


The first example of the ADMET polymerization of esters was
performed using the tungsten catalyst, 2b (Figure 2.2), and a







monomer possessing eight methylene spacers between the ester
functionality and the olefin.46 While this demonstrated the
viability of the ADMET polymerization of ester-containing olefins,
it did not address the limitations of these polymerizations. In order
to establish the synthesis rules and conditions for the
polymerization of these ester monomers, a study was undertaken
to determine the number of methylene spacers between the olefin
and the ester group required to allow a successful ADMET
polymerization.
Table 2.1 lists the unsaturated ester monomers with various
numbers of methylene spacers between the ester group and the
olefin used in this research. The polymerization of the linear alkyl
ester, ., demonstrates that monomers with as few as two
methylene spacers from the carbonyl side of the ester polymerize
successfully using the molybdenum catalyst, 1. The polymerization
proceeds rapidly at room temperature and exhibits no evidence of
chain transfer or branching in either the 1H or 13C NMR data as
well as the optimal MWD (molecular weight distribution) of 2.0 for
the polymerization. This polymerization also demonstrates the
ability to rapidly synthesize high molecular weight unsaturated
polyesters using the molybdenum catalyst, 1, at room
temperature.
By comparison, the analogous alkyl ester, 1, in which only one
methylene spacer is present, shows no evidence of metathesis
polymerization at either olefin site. This result is surprising since
one would have expected at some dimerization product from the
side with four methylene spacers present. This shows that the








Table 2.1. Unsaturated polyesters formed via the ADMET
polymerization.

Monomer IPolymer
o o o
0 0


oII (4) No Metesis
11 II 112111
O ( 4) (1 0)






S(6) No Metathesis




0
H No Metathesis
OC (8)






ester functionality with one methylene spacer is not inert, but

reacts quickly with the catalyst destroying its catalytic activity.

When Mo catalyst l is reacted with 14 at -800C at a 1:1 ratio in an

NMR experiment, a new peak in the alkylidene region was

observed at 12.1 ppm. This new alkylidene peak may have been


O O
+ [Mol-] CO Mo


Decomposition
Products


Figure 2.5. Possible reaction between 14 and catalyst la where
[Mo] is catalyst la.








been the new propagating species formed upon the addition of the
catalyst to the olefin; however, the new compound was very
unstable and decomposed before further analysis could be
performed (Figure 2.5). The experiment clearly showed that while
dimerization is not taking place, the ester functionality with only
one methylene spacer does react with the catalyst to yield some
non-metathesizing compound.
The number of methylene spacers between the ester
functionality and the olefin is a factor in these polymerizations and
this observation agrees with a similar study of monomers
containing the ether functionality.39,40 The minimum number of
methylene spacers between the olefin and the ester from the
oxygen side is also two for successful metathesis to occur, as
demonstrated with the aromatic esters 3-6. These comparisons
were made under identical reaction conditions. In some classical
catalyst systems, reactivity has been observed in systems with
only one methylene spacer present.45
There are two possible reasons for this lack of reactivity when
less than two methylene spacers are present and we term this
phenomenon the negative neighboring group effect. First, the ester
may polarize the olefin such that the successful formation and
decomposition of the metallocycles in the catalytic cycle are
hindered. Second, the carbonyl might coordinate with the metal
center. This coordination would result in the formation of five or
six member rings in the case of monomers and ., respectively,
which has been proposed in similar systems(Figure 2.6).47 The
coordination of the carbonyl with the metal center of a metalla-







Mo = CH
/ \
O CH2
C_ O/ Mo = CH

I O CH2
p I


II


Figure 2.6. The potential coordination of monomers and 6 leading
to coordinatively unsaturated metal centers.

cyclobutane resulting in four member rings has been observed in
similar systems.48
Varying the number of methylene spacers from two to four had
no obvious effect on the rate of polymerization; therefore, this
negative neighboring group effect appears exclusively in the one
methylene spacer cases. Regardless of the reason for the negative
neighboring group effect, it is clear that having less than two
methylene spacers between the olefin and the ester functionality
prevents polymerization.

Unsaturated Polyester Characterization and Molecular Weight
Analysis


Table 2.2 compiles the reaction temperature and the molecular
weight data for polymers 9-13. In all cases, the oligomers were
found to be perfectly linear and pure as demonstrated by the 13C
NMR spectra for polymer 9 in Figure 2.6. The trans Icis ratio found
in all of the polymers was similar to that observed in other ADMET








systems where the polymers were found to be 80-90 % trans.34 All
aromatic ester polymerizations were limited by the solubility of the
growing oligomer since these polymerizations ceased when the
oligomers precipitated from solution at both 25 and 450C.
The polymerizations of the aromatic ester monomers 3-5 were
carried out at 450C, a temperature at which the catalyst's reactive
intermediates begin to decompose. Consequently, multiple catalyst
additions produced higher molecular weight oligomers; however,
the active catalyst decomposed before a true equilibrium could be
established, leading to non-equilibrium molecular weight dis-


Table 2.2. Molecular weight data for unsaturated polyesters.


Polymer T (C) Xn Mn MWD

9 45 39 11,700 3.5
9 25 20 9,500 2.3
(9,200)

10 45 45 12,300 2.7
11 45 22 5,200 2.5

12 25 101 (18,400) 1.9

13 25 22 4,100 2.1



Refer to Table 2.1 for polymer structures. Mn in parenthesis
determined by VPO; all others determined by endgroup
analysis from 1H NMR. The molecular weight distribution
(MWD) was determined by gel permeation chromatography
relative to polystyrene. -







B E D

/ A 01









B
A A B
C D p



P (bm)
D B
A





160 140 120 100 8O 60 40 20 PPM

Figure 2.6. 13C NMR spectra for polymer 9. The spectra was
recorded using a 200 MHz instrument and CDCI3
as the solvent.


tributions. The molecular weight distributions shown in Table 2.2
are reflective of a step polymerization process.

In order to demonstrate the viability of copolymerizing the
aromatic esters with more flexible monomers, a copolymerization
was carried out with a 1:1 mixture of 1,9 decadiene and monomer 4
and was compared with a homopolymerization of monomer 4. The
homopolymerization of monomer 4 produced an average degree of
polymerization of 11, limited by the solubility of the growing
oligomers. An identical room temperature copolymerization
resulted an average degree of polymerization of 22. The significant
increase in molecular weight- at room temperature is attributed to







the introduction of a flexible unit. The copolymer is random in
nature.


Thermal Analysis of the Unsaturated Polyesters


The thermogravimetric analysis (TGA) data in Table 2.3 shows
that the unsaturated polyesters display a high degree of thermal
stability. In all cases the polymers exhibited total weight loss in a
single step as displayed in Figure 2.7, which is the thermogram for
polymer 11 and is representative of all the curves regardless of
nitrogen or air purge
The differential scanning calorimetry (DSC) results are depicted
in Table 2.4. No Tg is observed for polymers 9 and 11 above -500C

even at heating rates of 20 OC/min. This observation as well as the
sharpness of the transition peaks, imply a high degree of
crystallinity for polymers 9. and 11. A typical DSC curve for the
above mentioned polymers is displayed in Figure 2.8. Polymer 12
at slow ramp rates of 4 OC/min. shows very strong recrystallization
and melting peaks with no clear Tg. At 9 OC/min, however, the

crystallization peak decreases significantly, reappearing in the
heating cycle overlapping with the melting peak. At this rate a
clear Tg is observed. Polymers 10 and 13, which contain three
methylene spacers between the olefin and the aromatic peak,
exhibited very slow rates of crystallization; therefore, extrapolated
thermal data were difficult to obtain. A typical thermogram of
these two polymers consists of a weak melting transition upon









Table 2.3. Thermogravimetric analysis data for unsaturated
polyesters.

Onset (C) 90 % Weight Loss (*C)
Polymer
Air Nitrogen Air Nitrogen

9 251 326 487 410

10 245 335 495 418

11 291 323 500 422

12 199 257 463 480

13 278 283 489 446


All values were obtained at a 5C/min. heating rate.


Temperature (C)


Figure 2.7. TGA thermogram for polymer 11 obtained at a
5C/min. heating rate under a nitrogen purge.





33

Table 2.4. Differential scanning calorimetry data for unsaturated
polyesters.


Tm (oC)

101a,c

39b

162ac

-8c


Polymer

9

10

11

12

13


Tg is defined as the glass transition temperature, Tc as the
temperature of crystallization, and Tm as the temperature
of melting.
a: Values obtained at 20, 10, and 5C/min. and extrapolated
back to 0C/min.
b: Values determined from a 5C/min. cycle.
c: Values determined from a 40C/min. cycle.
d: Values determined from a 90C/min. cycle.
e: Bimodal with values corresponding to the inflection point of
the initial peak.
f: Peak possess shoulder.


initial heating and the absence of other transitions in the remainder

of the three cycles.


Kinetic Advantage of the Molybdenum Based Catalyst Versus that
of Tungsten


The molybdenum catalyst, 1, offers a kinetic advantage over


Tc (oC)

80a


-27


the tungsten catalyst, 2, in this chemistry.


When 1,9-decadiene


was exposed to the tungsten catalyst, 2b, in a 800:1 ratio, an olig-


Tg (OC)


-46b





34


0.6
S0 0
0.4 ocC0 Co C-0.





S0.0-
Iii



-0.2-


-0.4


-so so ideo o a 2o 2io
Temperature (OC)


Figure 2.8. DSC thermogram for polymer 11 obtained at a
heating rate of 5C/min.


omer of Xn=ll was produced within 3 hours, whereas, the

molybdenum catalyst, b., generated this oligomer in less than 5

minutes (Figure 2.9). This dramatic increase in reaction rate is

significant, and this phenomenon has been observed in similar
systems.20,49 This means that solution polymerization becomes a
reality since the polymerization can proceed at a reasonable rate
even when a growing polymer chain is diluted in solution. Thus,

the low temperature polymerization of stiffer and less soluble

polymers becomes viable.








Catalyst
Ns-##N # --^+


Figure 2.9. Kinetic comparison between molybdenum and tungsten
based catalysts performed as side by side reactions in
the drybox under identical conditions at 800 moles of
monomer/mole of catalyst.


Acyclic diene metathesis (ADMET) polymerization offers a
viable route for the synthesis of pure unsaturated polyesters. The
use of the highly active, Mo based, Lewis acid-free alkylidene
catalyst provides a clean route to unsaturated polyesters with
known vinyl endgroups. The polymerizability of a monomer is
limited by the number of methylene spacers between the ester
functionality and the olefin, a phenomenon which we term the

negative neighboring group effect. The observation that
molybdenum catalyst 1 successfully polymerizes acyclic dienes is
significant since it is more tolerant to polar functionalities and
reacts at a significantly faster rate than tungsten catalyst 2 for
some terminal olefins. The successful ADMET polymerization of
ester containing dienes led to the investigation of the carbonate and
the ketone functionalities. The following chapters address each of
these functional groups.


Catalyst Xn Time (min.)

[Mo](lb) 11 5
[W] (2b) 11 200














CHAPTER 3


ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE SYNTHESIS OF UNSATURATED POLYCARBONATES


The preparation of polycarbonates is well established, as is the
case with polyesters. This research targets a new synthetic route to
polycarbonates. The ADMET polymerization of carbonate containing
monomers further supports the evidence that monomers containing
the carbonyl functionality can be polymerized.
Commercial methods of preparing polycarbonates involve either
an ester interchange route carried out as a two-stage melt
polymerization process or a phosgene reaction carried out in a basic
solution (Figure 3.1).1 Recently the ring opening polymerization of
carbonate containing macrocycles has been reported as a route to
various functionalized polycarbonates (Figure 3.2).50-52 Poly-



+CI-CO-CI

HO O OH / -C- O
\ +00-co-0.0

Figure 3.1. Conventional synthesis of polycarbonate.

Figure 3.1. Conventional synthesis of polycarbonates.
















0
IC\ n

n = 1-20


Figure 3.2. Ring opening polymerization of polycarbonates.


carbonates have found many commercial applications involving
packaging, structural foam, and transparent glasses.
This chapter reports the successful ADMET polymerization of
carbonate containing monomers using the molybdenum based
catalyst Mo(CHCMe2Ph)(N-2,6-C6H3-i-Pr2)[OCCH3(CF3)212, la, and
to our knowledge, this is the first report of the metathesis of
unsaturated carbonates. Simple alkyl monomers have been used to
define the synthesis rules of the ADMET polymerization of
monomers containing the carbonate functionality (Figure 3.3). A
polymer containing the bisphenol linkage was also synthesized

0 O
OCO n Catalyst OCO + CH2=CH2



Figure 3.3. Simple unsaturated polycarbonates synthesized via the
ADMET polymerization.







O O
I /X II0 Catalyst
oc -O 0,oco


0 0
OC OCO + CH2=CH2

Figure 3.4. Unsaturated polycarbonate containing the bisphenol-A
linkage synthesized via ADMET chemistry.


demonstrating the polymerization of a highly functionalized
carbonate monomer (Figure 3.4).

ADMET Synthesis of Unsaturated Polycarbonates and the Negative
Neighboring Group Effect


In order to establish the synthesis rules and conditions for the
polymerization of these carbonate containing monomers, a study
was undertaken to determine the number of methylene spacers
required to allow a successful ADMET polymerization. A summary
of the monomers studied and the polymers formed is found in
Table 3.1.
Table 3.1 lists the unsaturated carbonate monomers with
various numbers of methylene spacers between the carbonate
group and the olefin used in this research. The polymerization of
the linear alkyl carbonate, 17, demonstrates that monomers with
as few as two methylene spacers between the carbonate function
ality and the olefin polymerize successfully using the molybdenum
catalyst. The polymerization proceeds rapidly at room temperature
and exhibits no evidence of chain transfer or branching in either






39

Table 3.1. Unsaturated polycarbonates synthesized via ADMET
polymerization.

Monomer Polymer

o 0
O (15) O (20)
oco X

0 [0
co^ (16) oo (21)
I -x
0
o (17) (22)
0
OCO (18) No Reaction
0 0 0
O O


(19) (23)


ality and the olefin polymerize successfully using the molybdenum

catalyst. The polymerization proceeds rapidly at room temperature

and exhibits no evidence of chain transfer or branching in either

the 1H NMR or 13C NMR as well as the optimal MWD (molecular

weight distribution) of 2.0. These polymerizations demonstrate the

ability to rapidly synthesize high molecular weight unsaturated

polycarbonates. By comparison, the alkyl carbonate, 18, in which

only one methylene spacer is present, shows no evidence of

metathesis.

The number of methylene spacers between the carbonate

functionality and the olefin is a factor in these polymerizations.

This observation agrees with similar studies of monomers

containing the ether and the ester functionalities (Chapter 2).39,40

The phenomenon of needing two methylene spacers between the






40

functionality and the olefin has been termed the negative
neighboring group effect, as described in the polyester chapter.


Unsaturated Polycarbonate Characterization and Molecular
Weight Analysis


Table 3.2 compiles the molecular weight and structural data for
polymers 20-23. In all cases, the oligomers were found to be
perfectly linear and pure as demonstrated by the 13C NMR for
polymer 23 in Figure 3.5. The translcis ratio found in polymers

20-22 was similar to that observed in other ADMET polymers. This
ratio for polymer 23 could not be determined since the cis signal
overlaps with the aromatic region in the 13C NMR spectra.
The gel permeation chromatography (GPC) data displayed in
Figure 3.6 is typical for step condensation polymerizations except


Table 3.2. Molecular weight data for unsaturated polycarbonates.


Polymer % Trans Mn Xn MWD

20 94 11,700' 52 2.0c
21 83 8600b 51 1.8c

22 89 8200' 58 2.0C

23 -- 15,800' 40 1.9c

Refer to Table 3.1 for polymer structures.
a: Determined by NMR endgroup analysis.
b: Determined by VPO.
c: Molecular weight distribution determined using
unprecipitated reaction mixture by gel permeation
chromatography relative to polystyrene.






41



CD G H
0 0o I

AB EF I


C
\


-CDCl3


140 120 inn r0 60 40 20 P


Figure 3.5.


13C NMR for polymer 23 obtained using a 200 MHz
instrument and CDCl3 as the solvent.


for the presence of the lower molecular weight fractions. In the

case of polymer 23 evidence of lower molecular weight cyclics was

observed both in the GPC trace as well as in the thermal analysis. A

polymerization of monomer 19 in a dilute solution enhanced the

formation of cyclics (Figure 3.6). The major product was again high

molecular weight polymer, however, significant fractions of low

molecular weight compounds were also evident. The 1H and 13C

NMR spectra of this material revealed the absence of vinyl


PM 0








0 0
^" ,o'..o o..o,,
4N, -iy0



4CuaWu~


0 0


Figure 3.6. GPC trace demonstrating the presence of low molecular
weight oligomers with the elution times being relative
to polystyrene arid THF as the solvent.







endgroups which are easily observed in ADMET polymerizations up
to a degree of polymerization of approximately 50 for linear chains.


Thermal Analysis of the Unsaturated Polycarbonates


The thermogravimetric analysis (TGA) data is shown in Table
3.3. Polymers 20-22 exhibited a large initial weight loss in a single
step. Polymer 23 showed an initial weight loss at 75C, however,
only 5% weight loss was observed up to 275C at which time a large
weight loss was observed (Figure 3.7). The reason for this initial
weight loss is presumably due to the presence of lower molecular
weight cyclics which are decomposing at lower temperatures than
the high molecular weight fraction.
The differential scanning calorimetry (DSC) data is shown in
Table 3.4. No Tg is observed for polymers 2.0 and 22 above -1000C.
Polymer 21 showed a Tg at -58C for a 5C/min. ramp rate. No
other transitions were observed between 150 and -1000C for this
polymer, however, due to the slow kinetics of crystallization.
Polymer 23 was measured between -100C and 60C (Figure 3.8).
The initial heating cycle showed a clear Tm after which the only
resolvable and reproducible transition was that of the Tg, due to
the slow kinetics of crystallization or possibly a trace amount of
cyclics not removed in the purification step.









Table 3.3.


Thermogravimetric analysis data for
unsaturated polycarbonates.


90 % Weight Loss (OC)


Onset (C)


Polymer


Air Nitrogen Air Nitrogen


455

445

495

490


222

235

222

70


360

414


460

445


Refer to Table 3.1 for polymer structures. All values obtained at
a 50C/min. heating rate.





100- 0 0



80-



60

2
*I


Trumpeture (C0


Figure 3.7. TGA thermogram for polymer 21 obtained at a 5C/min.
heating rate under a nitrogen purge.









Table 3.4.


Differential scanning calorimetry data for
unsaturated polycarbonates.


I Y Y
Polymer Tg (0C)


Polymer

20

21

22


23


Refer to Table 3.1 for polymer structures. Tg is defined
as the glass transition temperature, Tc as the temperature
of crystallization, and Tm as the melting temperature.
a: Values obtained at 20, 10, and 5C/min. and then
extrapolated back to 0C/min.
b: Values determined from 50C/min. cycle.

4-1


Heaing --


-60 -40 -20 0 20 40 60
Temperature (*C)


Tm (C)

77.8a


Tc (C)

57.5a


31.5a


Figure 3.8.


DSC thermogram for polymer 23 obtained from a
5C/min. heating rate under a nitrogen purge.


0.0-



-0.2-


-0.4-



-n -


w i


Tg (C)




-58.0b


-21.9a






46

Acyclic diene metathesis (ADMET) polymerization offers a
viable route for the synthesis of pure unsaturated polycarbonates.
The use of the highly active, Mo based, Lewis acid-free alkylidene
catalyst, la, provides a clean route to unsaturated polycarbonates
with known vinyl endgroups. The polymerizability of a monomer
is limited by the number of methylene spacers between the
carbonate functionality and the olefin, a phenomenon which we
term the negative neighboring group effect, which was first
observed in the case of the ester functionality. .The successful
polymerization of the ester and carbonate containing dienes
demonstrates that these functionalities can be metathesized
without the interference of Wittig-type chemistry. This led to the
investigation of ketone containing dienes since this functionality is
more susceptible to Wittig type chemistry than the ester or
carbonate groups.














CHAPTER 4


ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION:
THE SYNTHESIS OF UNSATURATED POLYKETONES


This chapter reports the successful synthesis of unsaturated
polyketones via the ADMET polymerization using the molybdenum
based catalyst Mo(CHCMe2Ph)(N-2,6-C6H3-i-Pr2)[OCCH3(CF3)212,

la. Unsaturated polyketones were not known prior to this work,
and the ADMET polymerization of ketone containing dienes
completes an investigation of the ADMET polymerization of
carbonyl containing monomers. The successful ADMET
polymerization of ester and carbonate containing dienes is
described in previous chapters.
The preparation of saturated polyketones is well established, as
is the case for polyesters and polycarbonates, and at least three
synthetic routes to saturated polyketones are known (Figure 4.1).53
Reaction 4.1.1 is generally initiated via free-radical chemistry to
produce random or alternating copolymers or by a nickel catalyst
resulting in perfectly alternating copolymers.53,54 Reaction 4.1.2 is
carried out under basic conditions demonstrating one of the few
examples of nucleophilic aromatic substitution successfully used in
polymer chemistry.55,56 Reaction 4.1.3 is performed under Friedel-
Crafts conditions which is also rarely successful in polymer
47








0
4.1.1) CH2=CHR + C O -CH2CHRC-



4.1.2) HO OH + F -C- F ---
OO x
0 ? 0 0 1



X


Figure 4.1. Conventional syntheses of polyketones.


chemistry.57,58 While these methods of polymer synthesis are rare,
nonetheless, these saturated polymers are successfully synthesized
and commercially important.


Synthesis of Unsaturated Polyketones


Acyclic diene metathesis (ADMET) polymerization augments the
chemistry discussed above by allowing the synthesis of unsaturated
polyketones.59 These ketone containing monomers were interesting
since the ketone functionality is more susceptible to the Wittig
type chemistry previously described (Figure 1.10) than the ester or
carbonate functionalities.







O 0
Catalyst
S+ CH2=CH2
R R2R R 4
RRR2RR


Figure 4.2. ADMET polymerization of tetraalkyl-keto-dienes.


Both homopolymerizations and copolymerizations have been
used in this research to synthesize the unsaturated polyketones
(Table 4.1). The homopolymerization of 24 resulted in the violent
evolution of ethylene as the rapid polymerization to 29 occurred.
Wittig-type chemistry does not interfere, likely due to steric
hinderence around the carbonyl group due to the presence of the
methyl groups. Evidence for this successful polymerization can be
seen in the conversion of monomer 27 to polymer 32
demonstrating the ability to synthesize high molecular weight
polymers. Monomer 27 does not possess the methyl groups and is
therefore less sterically hindered about the carbonyl group and, as
shown in Table 4.2, there is a very large decrease in the molecular
weight for this polymer.
Unsaturated polyketone copolymers were successfully obtained
via the copolymerization of 1,9-decadiene with a variety of
comonomers, and summary of the monomers studied and the
polymers formed is found in Table 4.1. These copolymerizations
proceed rapidly and exhibit no evidence of chain transfer or
branching in either the 1H NMR or 13C NMR. The polymers formed
also exhibit the optimal molecular weight distribution (MWD) of 2.0








Table 4.1. Unsaturated polyketones synthesizes via the ADMET
polymerization.


Mo nomer
X M Y Polymer

-^S^.X^^ ^ *~ I(29)
(24) (
0

(25) (30)



(26) (1)


o 0
(27) (32)






iru turns "



which is the expected value for clean step polymerizations. These

reactions demonstrate the ability to rapidly synthesize high

molecular weight unsaturated polyketones.


Unsaturated Polyketone Characterization and Molecular
Weight Analysis



Table 4.2 compiles the molecular weight and structural data for

polymers 2.9-33. In all cases, the oligomers were found to be

perfectly linear and pure demonstrating that unsaturated

polyketones with steric bulk around the carbonyl group can be







successfully synthesized using the ADMET polymerization The
trans/cis ratio found in polymers 29-33 was similar to that
observed for other ADMET polymers.34 The lower molecular
weights of polymers 32 and 33 was likely due to the presence of
trace amounts of mono-ene present in the reaction mixture.


Table 4.2. Molecular weight data for unsaturated polyketones.

I I I I I


Polymer

29

30

31

32

33


Y/X


n>5

>50

>50

13

5

13


g a


640

1,760


w b


16,400

30,600

5,000



4,900


MWDb

1.7

1.7

2.0

1.9

1.8


a: Determined by endgroup analysis from 1H NMR.
b: Determined by gel permeation chromatography
relative to polystyrene.


ADMET Cyclization of Ketone Containing Dienes


The attempted homopolymerization of compounds 34 and 3 5
produced an intriguing set of results. Rather than giving the
expected linear polymers, they were found to quantitatively
cyclize in the absence of solvent to give difunctional seven
membered rings (Figure 4.3). Molecular mechanics (MM2)
calculations support the hypothesis that the Thorpe-Ingold effect,






52

due to two pairs of gem-dimethyl groups adjacent to the carbonyl
carbon, is forcing the linear ketononadiene into a horseshoe
conformation inducing cyclization.60,61
Examples of substituted diene cyclizations by metathesis, even
in the presence of a solvent, are rare.62 A silacyclopentene ring
has been formed in low yield using an aluminum/rhenium catalyst
system, and five and six membered rings have been formed in the
intramolecular reaction of a tungsten carbene complex, where the
diene was one of the ligands.63,64 Cyclization of unsubstituted 1, 7-
dienes in various solvents has been reported, but complete
conversion occurs only in a few cases.1,65,66 Formation of cyclic
alkene oligomers from back-biting during the ROMP reaction is also
known.67 These cyclizations are unusual in that they are
intermolecular between catalyst and substrate and yield quantita-

0 O
Catalyst + CH2=CH2
-yy + CH--CH2

(34) (36)


0O

+ CH2=CH2



cis (37)
(35)


Figure 4.3. ADMET cyclization of Tetraalkyl-5-keto-1,8-nonadienes.








tive product solely from the monomer in the absence of solvent.
The dilute solution cyclization of ether containing dienes to five,
six, and seven-membered rings has recently been reported in
which, again, substitution alpha to the heteroatom is present
implying a Thorpe-Ingold effect.62
Ketodiene 34 cyclized to give tetramethylcycloheptanone 36
quantitatively in one hour total reaction time (Figure 4.3). The 1H
NMR of the cyclization of 34 is presented in Figure 4.4. An attempt
to copolymerize 34 with 1,9-decadiene yielded the entire amount of
34 cyclized while the 1,9-decadiene underwent an independent
ADMET homopolymerization to polyoctenomer. The polymer could
be separated from 36 by precipitation into methanol. The longer
diene 29 (see Table 4.1), however, gave only polymer, indicating
that a fairly rigid conformation of the diene is necessary for
cyclization. The unmethylated ketone 38 gave only a mixture of
linear oligomers in an NMR reaction (Figure 4.5). Cyclic ketodiene
35 also gave quantitative cyclization to the unusual bicyclic
ketoalkene 37 in a solventless reaction in one hour (Figure 4.3). As
in the linear case, the longer diene 26 (see Table 4.1) gave only
linear oligomers under the same reaction conditions.
These results suggest that the cyclization is brought about by
the Thorpe-Ingold effect as previously mentioned.68-70 MM2
calculations were run in order to find the local conformational
energy conditions.61 The two conformers of 34 are shown in Figure
4.6. Conformer 34a was found to be favored by 2.9 kcal/mole with
the distance between the terminal carbon atoms being 3.5 A,
while in 34b it is 9.3 A. This may explain why cyclization takes








place in the absence of solvent, and why the attempted
copolymerization was unsuccessful. In the case of the
unmethylated ketone 38, the analogous conformers were found to
be isoenergetic within 0.1 kcal/mole. If the first metathesis
reaction occurs after approach of the catalyst to the outside of the
horseshoe, only a single bond rotation is required to bring the
metal into close contact with the olefin moiety on the other side.
Mono-gem-disubstituted compounds were investigated in an
attempt to further demonstrate the potential synthetic utility of
these cyclizations (Figure 4.7). These compounds further support
the hypothesis that with the appropriate substitution cyclization
can be induced.
The cyclizations were performed using very small amounts of
reactants making it difficult to determine the true overall yield
possible. The use of NMR and GC/MS, however, verified that only
cyclized compound and no oligomerized product was present in the
cases of reactants 42, 43, 44, and 46. The attempted cyclization
of reactant 44 in a NMR reaction resulted in only linear polymer
with a degree of polymerization of at least 50 repeat units in ten
minutes. The rate of the polymerization under the dilute NMR
conditions indicates that cyclization is likely occurring followed by
the rapid ring opening metathesis polymerization (ROMP) of the
cyclic compound.













0
N

/


.Is-


4


ipp


Figure 4.4. 1H NMR of the cyclization of 34 to 36 after one hour
performed under drybox conditions.


-A


-r


I


. I I I I .. I P. .. I '








0



(38)


Catalyst


O
I /


+ CH2=CH2


(40)


Catalyst


trans


(39)


+ CH2=CH2


(41)


Figure 4.5.


Linear oligomerization of unmethylated keto-dienes.


34a


34b


"Horseshoe" and "crescent" conformers of 34.


Figure 4.6.













0


(47)


0



(42)


0

3 -Ph

(43)


(48)


MeO2C CO2Me



(49)


Me02C C02Me


(44)


O



(45)



0



(46)


(50)


(51)


Cyclization of mono-gem-disubstituted compounds.


Figure 4.7.








Summary


The use of the highly active, Mo based, Lewis acid-free
alkylidene catalyst, Ja, provides a clean route to unsaturated
polyketones as well as polyesters and polycarbonates with known
vinyl endgroups. This demonstrates the fact that the ADMET
polymerization may be utilized even in cases where highly polar
functional groups such as the carbonyl functionality are present.
These polymerizations were used to study structure, control in the
repeat unit and structure reactivity relationships.
In terms of the structure reactivity relationships of monomers
the ADMET synthesis of unsaturated polyesters and polycarbonates
exhibits a negative neighboring group effect. This negative
neighboring group effect involves either the coordination of the
carbonyl oxygen to the metal center or simply the polarization of
the double bond such that the intermediates of the metathesis
process are not favored. While this phenomenon has not been
studied for the ketone containing dienes it is likely that the same
effect would be observed.
Ketone containing dienes were shown to cyclize at very high
conversions when the appropriate substitutions are present. The
reason for the cyclizations is due to a Thorpe-Ingold effect where
the diene exists in a conformer which favors cyclization. These
cyclizations are a potentially powerful tool in the area of synthesis.














CHAPTER 5


EXPERIMENTAL


Monomer syntheses were performed under dry argon
atmosphere using standard Schlenk techniques. Toluene and
pentane were extracted with cold concentrated sulfuric acid
followed by basic potassium permanganate. Tetrahydrofuran
(THF), pentane, and toluene were distilled from potassium
benzophenone ketyl. The compounds Mo(CHCMe2R)(N-2,6-C6H3-i-
Pr2)[OCCH3(CF3)2]2 and W(CHCMe2R)(N-2,6-C6H3-i-Pr2)[OCCH3
(CF3)212, 1 and 2 (Figure 2), were prepared according to literature
methods.19'71 All other solvents and reagents were purged with
argon and used without further purification.
The ketone containing dienes 24-28, 34-35, 38-32, and 42-46
were synthesised by Dr. Malcolm Forbes and were used without
further purification.59 A sample synthesis of these ketones can be
seen in the synthesis of 4,4,6,6-tetramethyl-1,8-nonadiene-5-one,
34.
1H and 13C NMR spectra were recorded on a Varian VXR-300
(300 MHz) or a Varian XL-200 (200 MHz) spectrometer. NMR
data are listed as parts per million downfield from TMS. Obvious
multiplicities and routine coupling constants are not listed.
59







NMR spectra are obtained in CDC13 unless otherwise noted. IR data

was recorded on a Perkin Elmer 281 Infrared Spectrometer. Gel
permeation chromatography (GPC) analyses were carried out with
the use of Phenomenex Phenogel 5 500A and 5000A columns
coupled, a Waters Associates differential refractometer, and a
Perkin-Elmer LC-75 spectrophotometric detector on polymer
samples 0.1-0.3 % W/V in THF. The GPC columns were calibrated
versus commercially available polystyrene samples ranging from
910 to 1.10 x 105 g/mole. Vapor pressure osmometry was carried
out with the use of a Wescam 233 molecular weight apparatus at
500C on polymer samples ranging from 8 to 18 g/L in toluene.
Differential scanning calorimetry (DSC) was carried out using a
DuPont DSC 2910 Differential Scanning Calorimeter.
Thermogravimetric analysis (TGA) was carried out using a DuPont
Hi-Res TGA 2950 Thermogravimetric Analyzer. Elemental analyses
are by Atlantic Microlab, Inc., Atlanta, GA.


1.4 Benzene dicarboxylic bis (1-hexenyl) ester (3). Terephthaloyl
chloride (5.0 g, 0.025 moles) was purged with argon and then
dissolved in 50 mL of dry THF followed by the dropwise addition of

dry pyridine (3.90 g, 0.050 moles, exothermic) via a syringe. 5-
Hexene-1-ol (10.0 g, 0.10 moles) was added dropwise via a syringe
after which the mixture was heated to reflux for 3 hours under
argon. The THF was removed in vacuo. The residue was dissolved
in 50 mL of H20 and washed with 100 mL of diethyl ether. The

ether fractions were combined, washed once with 10% aqueous HC1,
and washed twice with 10% aqueous Na2CO3. Initial distillation via







short path distillation under full vacuum yielded the product as a
colorless oil (8.79 g, 92 %). Further purification for polymerization
of 3 was accomplished by distillation via short path distillation
under full vacuum onto CaH2 and stirred overnight followed by
filtration of the monomer through a celite bed with the aid of
pentane after which the pentane was removed in vacuo. The
monomer was then redistilled via short path distillation under full
vacuum into a roundbottom storage flask equipped with a Rotaflow
stopcock and molecular sieves. It had the following spectral
properties, IH NMR (CDC13), 1.54 (p, 2 H), 1.79 (p, 2 H), 2.12 (q,
2 H), 4.33 (t, 2 H), 4.91-5.10 (m, 2 H), 5.69-5.92 (m, 1 H), 8.08
(s, 2 H); 13C NMR (CDC13), 166.0, 138.2, 134.1, 129.1, 115.1,
65.5, 33.2, 27.8, 25.2. The IR spectrum (neat, KBr) showed
absorptions at: 2850, 1710, 1405, 1265 cm-1. Anal. Calcd. for
C20H2604: C, 72.70; H, 7.93. Found: C, 72.79; H, 7.95.


1.4 Benzene dicarboxylic bis (1-pentenyl) ester (4). Preparation of
4 from terephthaloyl chloride (5.0 g, 0.025 moles), pyridine (3.90
g, 0.050 moles), and 4-penten-l-ol (4.32 g, 0.050 moles) was
analogous to the procedure for 3 yielding the product as a colorless
oil (6.44 g, 94 %) with the following spectral properties: 1H NMR
(CDC13), 1.88 (p, 2 H), 2.21 (q, 2 H), 4.35 (t, 2 H), 4.95-5.14 (m,

2 H), 5.72-5.97 (m, 1 H), 8.08 (s, 2 H); 13C NMR (CDC13), 166.0,
137.8, 134.1, 129.8, 115.7, 64.9, 30.0, 28.0. The IR
spectrum (neat, KBr) showed absorptions at: 2850, 1715, 1405,
1265 cm-1. Anal. Calcd. for C18H2204: C, 71.50; H, 7.33. Found:
C, 71.38; H, 7.31.








1.4 Benzene dicarboxylic bis(1-butenyl) ester (5). Preparation of 5
from teraphthaloyl chloride (12.50 g, 0.0246 moles), pyridine
(9.81 g, 0.124 moles), and 1-butenol (10.0 g, 0.139 moles) was
analogous to the procedure for 3 yielding the product as a colorless
oil (15.03 g, 89 %) with the following spectral properties: 1H NMR
(CDC13), 2.50 (q, 2 H), 4.37 (t, 2 H), 5.02-5.21 (m, 2 H), 5.72-
5.97 (m, 1 H), 8.08 (s, 2 H); 13 C NMR (CDC13) 165.9, 134.0,
133.9, 129.9, 117.6, 64.2, 33.1. The IR spectrum (neat, KBr)
showed absorptions at: 2900, 1720, 1640, 1405, 1265 cm-1.
Anal. Calcd. for C16H1804: C, 70.06; H, 6.61. Found: C, 69.96; H,
6.65.


1.4 Benzene dicarboxylic bis (1-propenyl) ester (6). Preparation of
6 from teraphthaloyl chloride (5.0 g, 0.025 moles), pyridine (3.9 g,
0.05 moles), and allyl alcohol (3.9 g, 0.05 moles) was analogous to
the procedure for 3 yielding the product as a colorless oil (5.27 g,
87 %) with the following spectral properties: IH NMR (CDC13), 4.83
(dd, 2 H), 5.24-5.48 (m, 2 H), 5.92-6.15 (m, 1 H), 8.11 (s, 2 H);
13 C NMR (CDC13) 165.7, 134.1, 132.0, 129.9, 118.9, 66.0. The IR

spectrum (neat, KBr) showed absorptions at: 2800, 1720, 1650,
1405, 1265 cm-1. Anal. Calcd. for C14H1404: C, 68.28; H, 5.73.
Found: C, 68.15; H, 5.66.


1-Hexene-l-pentenoate (7). 1-Pentenoic acid (10.0 g, 0.10 moles),
5-hexene-l-ol (9.0 g, 0.090 moles), and 5 drops of concentrated
H2SO4 were refluxed in 150 mL of benzene in a Dean-Stark
apparatus for 12 hours with the occasional removal of H20. The








benzene was removed in vacuo, and the remaining oil was mixed
with 50 mL of diethyl ether and washed with a 10% Na2C03
solution (3 x 50mL) followed by one wash with a NaCI solution. The
ether solution was dried over MgSO4, filtered, and the ether
removed in vacuo. The resulting oil was then distilled via short
path distillation under a static vacuum into a flask containing CaH2
and stirred for 12 hours. The mixture was filtered through a celite
bed with the aid of pentane after which the pentane was removed
in vacuo. The colorless oil was redistilled via short path distillation
under static vacuum into a storage flask equipped with a Rotaflow
stopcock and molecular sieves (14.75 g, 81 %) with the following
spectral properties: 1H NMR (CDC13), 1.47-1.54 (m, 1 H), 1.54-
1.71 (m, 1 H), 2.07 (q, 1 H), 2.38 (s, 2 H), 4.07 (t, 1 H), 4.84-
5.11 (m, 2 H), 5.67-5.92 (m, 1 H); 13 C NMR (CDC13) 173.2,
138.5, 136.9, 128.6, 115.6, 114.8, 64.2, 33.8, 33.6, 29.6, 28.3,
25.8. The IR spectrum (neat, KBr) showed absorptions at: 2850,
1735, 1640, 1170 cm-1 Anal. Calcd. for C11H1804: C, 72.49; H,
9.95. Found: C, 72.48; H, 9.92.


1-Hexene-l-butenoate (8). Preparation of 8 from vinyl acetic acid
(5.0 g, 0.058 moles), 5-hexene-l-ol (5.23 g, 0.052 moles), and 5
drops of concentrated H2SO4 was analogous to the procedure for 7
yielding the product as a colorless oil (7.53 g, 77 %) with the
following spectral properties: 1H NMR (CDC13), 1.37-1.52 (m, 1 H),
1.52-1.72 (m, 1 H), 1.98-2.16 (q, 1 H), 3.01-3.16 (d, 1 H), 4.00-
4.19 (t, 1 H), 4.90-5.26 (m, 2 H), 5.68-6.04 (m, 1 H); 13 C NMR
(CDC13) 171.8, 138.1, 130.9, 128.3, 118.5, 115.1, 65.0, 39.4,







33.2, 28.0, 25.2. The IR spectrum (neat, KBr) showed absorptions
at: 2850, 1740, 1640, 1070 cm-1 Anal. Calcd. for C10H1602: C,
71.38; H, 9.59. Found: C, 71.10; H, 9.64.


Polv(oxy-5-decene-oxvteraphthalovl) (9). In a nitrogen filled
drybox, .la (0.01 g, 1.54 x 10-5 moles) was weighed into a Schlenk
tube equipped with a stopcock and two addition arms with
breakseals for additional catalyst additions. Each of the breakseal
containers was charged with la (0.005 g, 7.67 x 10-6 moles)
dissolved in 1.5 mL of toluene. Compound 3 (2.0 g, 6.05 x 10-3
moles) was then added to the catalyst in the Schlenk tube and the
mixture stirred. Rapid evolution of ethylene was observed and the
reaction mixture became solid within 5 minutes. Toluene (20mL)
was then added to the mixture which was then sealed, removed
from the drybox, and attached to a vacuum line where the system
was exposed to a slight vacuum to aid in the removal of ethylene.
The reaction mixture was then slowly warmed to 450C and allowed
to stir under a static vacuum. At 3 hour intervals, each of the 2
breakseals were broken. The initial catalyst to monomer ratio was
400:1. Three hours after the second catalyst addition, compound 9
was purified by dissolution in warm toluene followed by the
dropwise addition of the polymer solution into rapidly stirring
methanol at 0C. The white precipitate was then separated from
the solvents by centrifugation followed by the decanting of the
solvents yielding 9 as a white powder (1.66 g, 92 %) with the
following spectral properties: 1H NMR (200 MHz, CDC13), 1.54 (p,
2 H), 1.79 (p, 2 H), 2.12 (q; 2 H), 4.33 (t, 2 H), 4.91-5.10 (m, 2







H), 5.38-5.49 (br, 1 H), 5.69-5.92 (m, 1 H), 8.08 (s, 2 H); 13 C
NMR (50 MHz, CDC13) 166.0, 134.3, 130.4, 129.8, 129.7, 65.5,
32.0, 28.1, 25.9. The IR spectrum (film, KBr) showed absorptions
at: 2825, 1705, 1450, 1265 cm-1 Anal. Calcd. for C18H2204: C,
71.50; H, 7.33. Found: C, 68.79; H, 7.41.


Room Temperature Synthesis of 9. In a drybox equipped with
nitrogen atmosphere 1a (0.01 g, 1.53 x 10-5 moles) was weighed
into a Schlenk tube equipped with a stopcock followed by 3 (2.0 g,
6.05 x 10-3 moles). Rapid evolution of ethylene was observed and
the reaction mixture became solid within 5 minutes. The solid was
then dissolved in 20 mL of toluene and allowed to stir for an
additional 8 hours in a closed reaction vessel. The oligomers were
purified as in the 45 OC case (1.74 g, 95 %).


Poly(oxy-4-octene-oxvteraphthaloyl) (10). Preparation of 10 from
la (0.011 g, 1.65 x 10-5 moles) in the Schlenk tube and la (0.005
g, 7.67 x 10-6 moles) in each of the 2 breakseals was analogous to
the procedure for 9 (45 OC case) with 4 (2.0 g, 0.00661 moles) to
yield 10 as a white powder (1.53 g, 94 %) with the following
spectral properties: 1H NMR (CDC13), 1.88 (p, 2 H), 2.21 (br, 2 H),
4.35 (t, 2 H), 4.95-5.14 (m, 2 H), 5.45-5.57 (br, 1 H), 5.72-5.97
(m, 1 H), 8.08 (s, 4 H); 13C NMR (CDC13) 166.0, 134.2, 130.0,
129.8, 65.0, 28.9, 28.5. The IR spectrum (film, KBr) showed
absorptions at: 2875, 1710, 1445, 1265 cm-1 Anal. Calcd. for
C16H1804: C, 70.06; H, 6.61. Found: C, 68.40; H, 6.70.







Poly(oxy-3-hexene-oxyteraphthaloyl) (11). Preparation of 11 from
la (0.012 g, 1.82 x 10-5 moles) in the Schlenk tube and la (0.005
g, 7.67 x 10-6 moles) in each of the 2 breakseals was analogous to
the procedure for 9 with 5 (2.0 g, 0.00729 moles) to yield
poly(oxy-3-hexene-oxyteraphthaloyl) as a white powder (1.62 g,
90 %) with the following spectral properties: 1H NMR (CDC13),
2.40-2.65 (br, 2 H), 4.4.25-4.45 (t, 2 H), 5.57-5.73 (br, 1 H),
7.95-8.15 (s, 2 H); 13 C NMR (CDC13) 165.9, 134.1, 129.8, 128.7,
126.9, 64.6, 32.1. The IR spectrum (film, KBr) showed
absorptions at: 3100, 1705, 1405, 1250 cm-1 Anal. Calcd. for
C14H1404: C, 68.28; H, 5.73. Found: C, 66.23; H, 5.73.


Polyroxy-(3-octene)-esterl (12). In a drybox equipped with
nitrogen atmosphere la (0.018 g, 2.74 x 10-5 moles) was weighed
into a Schlenk tube equipped with a stopcock followed by 1 (2.0 g,
0.011 moles). Rapid evolution of ethylene was evident and the
reaction was allowed to stir until the reaction mixture became too
thick to stir after which 2 mL of toluene was added. The reaction
vessel was then closed off to the atmosphere, removed from the
drybox, and attached to a vacuum line where a static vacuum was
applied and the reaction mixture allowed to stir for an additional 8
hours (1.68 g, 99%). It had the following spectral properties: 1H
NMR (CDC13), 1.37-1.52 (m, 1 H), 1.52-1.72 (m, 1 H), 1.92 2.16
(br, 1 H), 2.16-2.50 (br, 2 H), 3.93-4.20 (t, 1 H), 5.27-5.60 (br, 1
H); 13 C NMR (CDC13) 173.4, 131.2, 130.4, 129.6, 128.8, 64.4,
34.3, 34.2, 32.2, 28.1, 28.0, 26.0, 25.9. The IR spectrum (film,








KBr) showed absorptions at: 2725, 1735, 1160, 965 cm-1 Anal.
Calcd. for C9H1402: C, 70.10; H, 9.15. Found: C, 69.18; H, 9.18.


Attempted polymerization of (8). 1 a (0.019 g, 2.97 x 10-5 moles)
and 8 (2.0 g, 0.012 moles) were reacted in an analogous procedure
for the synthesis of 12. Upon addition of the monomer to the
catalyst there was no apparent evolution of ethylene and after 3
hours 1H NMR revealed only unreacted starting material.


Copolymerization of 4 and 1.9-Decadiene (13). 4 (0.50 g, 0.0017
moles) and 1,9-decadiene (0.22 g, 0.00165 moles) were mixed
together and then added to a Schlenk tube preloaded with 1a
(0.005 g, 8.27 x 10-6 moles). Rapid evolution of ethylene was
observed. Within 15 minutes the reaction mixture went solid after
which 20 mL of toluene was added to dissolve the mixture which
was then allowed to stir for an additional 8 hours. The reaction
flask was then removed from the drybox and the polymer purified
as described for the aromatic homopolymers. It had the following
spectral properties: 1H NMR (CDC13), 1.18-1.45 (s, 2 H), 1.72-2.08

(m, 1 H), 4.23-4.41 (t, 1 H), 5.27-5.56 (m, 1 H), 8.02-8.17 (s, 1
H); 13C NMR (CDC13), 166.0,. 134.2, 131.9, 130.2, 130.0, 129.6,
129.2, 128.7, 128.3, 128.0, 125.5, 64.5, 32.6, 29.8, 29.7, 29.0,
28.9, 28.4, 28.3. The IR spectrum (neat, KBr) showed absorptions
at: 2810, 1720, 1410, 1265 cm-1 Anal. Calcd. for C24H3304: C,
74.77; H, 8.63. Found: C, 73.80; H, 8.44.







Benzene carboxylic (1-propenvl) ester (14). Preparation of 14 from
benzoyl chloride (10.97 g, 0.0783 moles), pyridine (6.81 g, 0.0861
moles), and allyl alcohol (5.00 g, 0.0861 moles) was analogous to
the procedure for 3 yielding the product as a colorless oil (12.1 g,
95%) with the following spectral properties: 1H NMR (d8-toluene),
4.75-4.90 (m, 2 H), 5.20-5.55 (m, 2 H), 5.80-6.20 (m, 1 H), 7.20-
7.50 (m, 3 H), 8.20-8.35 (m, 2 H); 13 C NMR (dg-toluene) 166.6,
138.4, 129.8, 129.4, 118.6, 66.3. The IR spectrum (neat, KBr)
showed absorptions at: 3200, 2890, 1725, 1605, 1370 cm-1.


Bis (1-hexenyl) carbonate (15). 5-Hexene-l-ol (10.0 g, 0.0998
moles), dimethylcarbonate (4.047 g, 0.0449 moles), and LiH
(0.020 g, 0.00252 moles) were all added to a dry and argon purged
100 mL roundbottom flask equipped with a flash distillation
apparatus. Methanol was then distilled from the mixture under
argon until no more methanol was recovered. The flash distillation
apparatus was then replaced by a standard fractional distillation
apparatus and the fractional distillation continued under vacuum.
The product was then stirred over CaH2 overnight after which the
mixture was filtered under argon over a celite bed with the aid of
dry pentane. The pentane was then stripped off of the mixture
which was then vacuum transferred into a roundbottom storage
flask equipped with a Rotaflow stopcock and molecular sieves as a
colorless oil (6.61 g, 65%) with the following spectral properties:
1H NMR (CDC13), 1.40-1.55 (m, 2 H), 1.64-1.77 (m, 2 H), 2.04-
2.17 (q, 2 H), 4.10-4.20 (t, 2 H), 4.93-5.09 (m, 2 H), 5.72-5.88
(m, 1 H); 13C NMR (CDCI3), 155.1, 137.9, 114.5, 67.5, 32.9,








27.8, 24.7. The IR spectrum (neat, KBr) showed absorptions at:
2925, 1750, 1640, 1260 cm-1. Anal. Calcd. for C13H2203: C,
68.99; H, 9.80. Found: C, 68.93; H, 9.83.


Bis (1-pentenyl) carbonate (16). Preparation of 16 from 4-
pentene-1-ol (10 g, 0.1161 moles), dimethylcarbonate (4.706 g,
0.0522 moles), and LiH (0.02 g, 0.00252 moles) was analogous to
the procedure for 15 yielding the product as a colorless oil (6.21 g,
60%) with the following spectral properties: 1H NMR (CDC13), 1.72-
1.84 (p, 2 H), 2.10-2.21 (p, 2 H), 4.10-4.20 (t, 2 H), 4.96-5.11 (m,
2 H), 5.72-5.89 (m, 1 H); 13C NMR (CDC13), 155.0, 137.0, 115.1,
67.0, 29.5, 27.5. The IR spectrum (neat, KBr) showed absorptions
at: 2960, 1750, 1645, 1260 cm-1. Anal. Calcd. for C11H1803: C,
66.64; H, 9.15. Found: C, 66.76; H, 9.10.


Bis (1-butenyl) carbonate (17). Preparation of 17 from 3-butene-
1-ol (10.0 g, 0.1387 moles), dimethyl carbonate (5.62 g, 0.0624
moles), and LiH (0.02 g, 0.00252 moles) was analogous to the
procedure for 15 yielding the product as a colorless oil (7.0 g, 66%)
with the following spectral properties: 1H NMR (CDC13), 2.39-2.48
(m, 2 H), 4.14-4.23 (t, 2 H), 5.08-5.20 (m, 2 H), 5.72-5.88 (m, 1
H); 13C NMR (CDC13), 154.8, 133.1, 117.3, 66.5, 32.7. The IR
spectrum (neat, KBr) showed absorptions at: 2970, 1750, 1645,
1260 cm-1. Anal. Calcd. for C9H1403: C, 63.51; H, 8.29. Found: C,
63.56; H, 8.26.








Bis (1-propenyl) carbonate (18). Preparation of 18 from allyl
alcohol (10.0 g, 0.1722 moles), dimethylcarbonate (6.97 g, 0.0775
moles), and LiH (0.02 g, 0.00252 moles) was analogous to the
procedure for 15 yielding the product as a colorless oil (5.51g, 50%)
with the following spectral properties: 1H NMR (CDC13), 4.53-4.63
(m, 2 H), 5.18-5.40 (m, 2 H), 5.80-6.02 (m, 1 H); 13C NMR
(CDC13), 154.8, 131.5, 118.7, 60.4. The IR spectrum (neat, KBr)
showed absorptions at: 2950, 1750, 1650, 1260 cm-1. Anal.
Calcd. for C7H1003: C, 59.14; H, 7.09. Found: C, 59.03; H, 7.10.

1. 4-Phenylene-iso-propvlidene-1, 4-phenylene-bis (1-butenyl)
carbonate (19). 4-Butene-l-ol (4.94 g, 0.0686 moles) and pyridine
(5.42 g, 0.0686 moles) were added to a dry 250 mL Schlenk tube
and stirred under argon at OOC in 50 mL of dry THF. 4, 4'-
Isopropylidenediphenol bis (chloroformate) (10.0 g, 0.0286 moles)
dissolved in 50 mL of dry THF was then added dropwise via an
addition funnel after which the mixture was allowed to stir for an
additional 2 hours at room temperature. The solvent was then
removed in vacuo resulting in a thick yellow oil. The oil was then
dissolved in enough toluene to allow transfer by pipet to a 6 inch
silica gel column (100-200 mesh) and the product eluted using
toluene-hexane (1/1) solvent. The solvent was then removed in
vacuo and the resulting colorless opaque oil left under vacuum for
8 additional hours to remove any excess 4-butene-l-ol and
pyridine. The oil was then dissolved in enough toluene to allow
effective stirring in CaH2 overnight. The mixture was then filtered
under argon through a celite bed with the aid of dry toluene. The







toluene was then removed in vacuo resulting in the product as a
colorless, opaque oil (8.3 g, 68%) with the following spectral
properties: 1H NMR (CDC13), 1.58-1.75 (s, 3 H), 2.41-2.59 (q, 2
H), 4.22-4.35 (t, 1 H), 5.08-5.25 (m, 2 H), 5.71-5.96 (m, 1 H),
7.0-7.3 (m, 4 H); 13C NMR (CDC13), 153.8, 149.0, 148.0, 133.3,
127.9, 120.5, 117.9, 67.7, 42.5, 33.0, 30.9. The IR spectrum
(neat, KBr) showed absorptions at: 2975, 1770, 1640, 1250 cm-1
Anal. Calcd. for C25H2806: C, 70.74; H, 6.64. Found: C, 70.80; H,
6.66.


Poly (5-decene) carbonate (20). In a drybox under a nitrogen
atmosphere the molybdenum catalyst (0.012 g, 2.209 x 10-5 moles)
was weighed into a Schlenk tube equipped with a stopcock followed
by 15 (2.0 g, 8.8 x 10-3 moles). Rapid evolution of ethylene was
evident and the reaction was allowed to stir until the reaction
mixture thickened after which 2 mL of toluene was added. The
reaction vessel was then closed off to the atmosphere, removed
from the drybox, and attached to a vacuum line where a static
vacuum was applied and the reaction mixture allowed to stir for an
additional 8 hours. The reaction mixture which was then diluted
with benzene (50 mL) and extracted with a sodium carbonate
solution (3 x 50 mL) followed by water. The benzene fraction was
then slowly added to a stirring solution of methanol precipitating
the polymer as a white solid which was isolated via centrifugation.
A vacuum was then applied to the polymer for a period of 24 hours
resulting in the product as a white powder (1.6 g, 93%) with the
following spectral properties: -1H NMR (CDC13), 1.25-1.51 (p, 2 H),








1.51-1.75 (p, 2 H), 1.88-2.10 (m, 2 H), 4.0-4.18 (t, 2 H), 5.28-
5.42 (m, 1 H); 13C NMR (CDC13), 155.4, 130.2, 129.6, 67.8, 32.0,
28.1, 25.7. The IR spectrum (film, KBr) showed absorptions at:
2900, 1745, 1260 cm-1. Anal. Calcd. for CllH1803: C, 66.64; H,
9.15. Found: C, 65.85; H, 9.11.


Poly (4-octene) carbonate (21). Preparation of 21 from the catalyst
(0.0132 g, 2.52 x 10-5 moles) in the Schlenk tube was analogous to
the procedure for 20 with 16 (2.0 g, 1.01 x 10-2 moles) to yield
poly (4-octene) carbonate as an opaque, highly viscous oil (1,46 g,
85%) with the following spectral properties: 1H NMR (CDC13), 1.60-
1.82 (p, 2 H), 1.95-2.18 (m, 2 H), 4.0-4.2 (t, 2 H), 5.30-5.51 (m,
1 H); 13C NMR (CDC13), 155.3, 129.8, 67.3, 28.6, 28.4,. The IR
spectrum (film, KBr) showed absorptions at: 2950, 1750, 1360
cm-1. Anal. Calcd. for C9H1403: C, 63.51; H, 8.29. Found: C,
63.59; H, 8.29.


Poly (3-hexene) carbonate (22). Preparation of 22 from the
catalyst (1.53 x 10-2 g, 2.94 x 10-5 moles) in the Schlenk tube was
analogous to the procedure for 20 with 17 (2.0 g, 1.18 x 10-2
moles) to yield poly(3-hexene)carbonate as a white solid (1.57 g.,
94%) with the following spectral properties: 1H NMR (CDC13), 2.22-
2.48 (m, 2 H), 4.0-4.2 (t, 2 H), 5.45-5.60 (m, 1 H); 13C NMR
(CDC13), 155.1, 128.1, 67.2, 31.9. The IR spectrum (film, KBr)
showed absorptions at: 2960, 1745, 1260 cm-1. Anal. Calcd. for
C7H1003: C, 59.14; H, 7.09. Found: C, 57.49; H, 7.23.








Attempted polymerization of 18. Catalyst (0.020 g, 3.84 x 10-7
moles) and 18 (1.0 g, 7.04 x 10-3 moles) were reacted in an
analogous procedure for the synthesis of 20. Upon addition of the
monomer to the catalyst there was no apparent evolution of
ethylene and after 3 hours 1 H NMR revealed only unreacted
starting material.


Polv(oxycarbonyloxy-1. 4-phenylene-iso-propylidene-1, 4-phenyl-
ene-oxycarbonyloxv-3-hexene) (23). Monomer 19. (2.0 g, 4.71 x
10-3 moles) and toluene (2 mL) were mixed together to allow
efficient stirring of the monomer and then added to a Schlenk tube
preloaded with catalyst (0.010 g, 1.92 x 10-5 moles). Rapid
evolution of ethylene was evident and the reaction was allowed to
stir until the reaction mixture thickened after which 2 mL of
toluene was added. The reaction vessel was then closed off to the
atmosphere, removed from the drybox, and attached to a vacuum
line where a static vacuum was applied and the reaction mixture
allowed to stir for an additional 8 hours. Benzene (50 mL) was then
added to dilute the reaction mixture which was then extracted with
a sodium carbonate solution (3 x 50 mL) followed by water. The
benzene fraction was then slowly added to a stirring solution of
methanol precipitating the polymer as a pale yellow solid which
was isolated via centrifugation. A vacuum was then applied to the
polymer for a period of 24 hours resulting in the product as a pale
yellow solid (1.76 g, 94%) with the following spectral properties:
1H NMR (CDC13), 1.55-1.80 (s, 3 H), 2.38-2.64 (m, 2 H), 4.16-4.38
(t, 2 H), 5.54-5.72 (m, 1 H), 7.0-7.38 (m, 4); 13C NMR (CDC13),








153.7, 149.0, 148.0, 128.2, 127.9, 120.5, 67.9, 42.5, 31.9, 30.9.
The IR spectrum (film, KBr) showed absorptions at: 2970, 1770,
1240 cm-1. Anal. Calcd. for C23H2406: C, 69.68; H, 6.10. Found:
C, 67.99; H, 6.21.


Dilute solution polymerization of 19. The polymerization was
analogous to the procedure for the synthesis of 23, however, 19
(1.0 g, 2.36 x 10-3 moles) was dissolved in 10 mL of toluene before
the addition of catalyst.


Poly[l-oxo-2.2.11.1 1-tetramethyl-6-undecenylenel (29). In a
drybox equipped with nitrogen atmosphere la (0.020 g, 3.84 x 10-
5 moles) was weighed into a Schlenk tube equipped with a stopcock
followed by 6,6,8,8-tetramethyl-1,12-tridecene-7-one, 24 (2.0 g,
8.0 x 10-3 moles). Rapid evolution of ethylene was evident and the
reaction was allowed to stir until the reaction mixture became too
thick to stir after which 2 mL of toluene was added. The reaction
vessel was then closed off to the atmosphere, removed from the
drybox, and attached to a vacuum line where a static vacuum was
applied and the reaction mixture allowed to stir for an additional 8
hours. The polymer was purified by first dissolving it in hexane
followed by extraction with brine and sodium carbonate solutions.
Removal of the hexanes resulted in the isolation of the polymer as
an pale yellow solid (1.69, 95 %) with the following spectral
properties: 1H NMR (CDCl3), 1.05-1.28 (s, 18 H), 1.40-1.57 (m, 2
H), 1.8-2.0 (m, 2 H), 5.25-5.36 (m, 1 H); 13 C NMR (CDC13) 131.0,
129.0, 49.5, 41.5, 33.2, 26.2, 25.0.







Poly (7-oxo-6.6.8.8-tetramethyl- 1 -undecenvlene)-co- 1 -octenylenel
(30). In a drybox equipped with nitrogen atmosphere la (0.020 g,
3.84 x 10-5 moles) was weighed into a Schlenk tube equipped with
a stopcock followed by a premixed solution of 6,6,8,8-tetramethyl-
1,12-tridecene-7-one, 25 (0.500 g, 2.00 x 10-3 moles) and 1, 9-
decadiene (0.276 g, 2.00 x 10-3 moles). Rapid evolution of ethylene
was evident and the reaction was allowed to stir until the reaction
mixture became too thick to stir after which 2 mL of toluene was
added. The reaction vessel was then closed off to the atmosphere,
removed from the drybox, and attached to a vacuum line where a
static vacuum was applied and the reaction mixture allowed to stir
for an additional 8 hours. The polymer was purified by first
dissolving it in hexane followed by extraction with brine and
sodium carbonate solutions. Removal of the hexanes resulted in the
isolation of the polymer as an pale yellow solid (1.2 g, 92 %) with
the following spectral properties: 1H NMR (CDC13), 1.10-1.22 (s, 4
H), 1.22-1.40 (s, 2 H), 1.44-1.58 (m, 1 H), 1.84-2.06 (m, 2 H),
5.27-5.42 (m, 1 H); 13C NMR (CDC13) 125.4, 125.2, 125.0, 214.8,
48.5, 41.2, 33.1, 32.8, 29.8, 29.1, 27.8, 27.2, 26.1, 24.9.


Poly(1 -hexenylene-1,3 -dimethyl- 1.3-c yclododecylene-2-oxo-3-
propylene)-co-l-octenylenel (31). Preparation of 31 from catalyst
la.(0.020 g, 3.84 x 10-5 moles) in the Schlenk tube was analogous
to the procedure for 30 with a premixed solution of 2,12-(bis-5-
pentene)-2,12-dimethyl-cyclododecyl-l-one, 26 (0.415 g, 1.20 x
10-3 moles) and 1, 9-decadiene (1.0 g, 7.2 x 10-3 moles) to yield 31

as a pale yellow solid (1.1 "g, 95 %) with the following spectral







properties: 1H NMR (CDC13), 1.05-1.60 (br. s, 20 H), 1.75-2.10 (br.
m, 8 H), 5.29-5.55 (m, 7 H); 13C NMR (CDC13), 218.0, 139.1,
130.6, 130.3, 130.1, 129.8, 114.1, 53.3, 39.1, 33.8, 33.4, 32.6,
29.7, 29.6, 29.3, 29.2, 29.0, 28.9, 27.4, 27.2, 27.0, 24.6, 23.8,
23.6, 20.8. The IR spectrum (film, KBr) showed absorptions at:
2930, 2852, 2361, 2345, 1680, 1462, 1257, 968 cm-1.


Poly [(1-propylene- 1.3 -cycloddecvlene-2-oxo-3-propylene)-co-1-
octenylenel (32). Preparation of 32 from catalyst la. (1.53 x 10-2 g,
2.94 x 10-5 moles) in the Schlenk tube was analogous to the
procedure for 30 with a premixed solution of 2,12-(bis-3-propene)-
cyclododecyl-1-one, 27 (1.00 g, 3.81 x 10-3 moles) and 1,9-
decadiene (3.17 g, 2.29 x 10-2 moles) to yield 32 as a pale yellow
solid (3.13 g., 92 %) with the following spectral properties: IH NMR
(CDC13), 1.10-1.45 (s, 13 H), 1.85-2.10 (m, 4 H), 5.28-5.45 (m, 1
H); 13C NMR (CDC13), 217.0, 139.1, 130.3, 129.8, 114.1, 49.3,
33.8, 33.7, 32.6, 29.7, 29.6, 29.4, 29.2, 29.0, 28.9, 28.3, 27.2,
25.4, 24.6, 22.0.


Poly [( 1-propylene-trans- 1.3 -dimethyl- 1.3-cyclododecylene-2-oxo-
3-methylene)-co-1-octenylenel (33). Preparation of 33 from
catalyst la. (1.53 x 10-2 g, 2.94 x 10-5 moles) in the Schlenk tube
was analogous to the procedure for 30 with a premixed solution of
trans-2,12-(bis-3-propene)-2,12-dimethyl-cyclododecyl- 1-one, 28
(0.194 g, 6.68 x 10-4 moles) and 1, 9 decadiene (0.462 g, 3.34 x
10-3 moles) to yield 3. as a pale yellow solid (0.52 g., 95 %) with
the following spectral properties: 1H NMR (CDC13), 1.05-1.10 (s, 3








H), 1.12-1.48 (s, 14 H), 1.85-2.12 (s, 4 H), 5.29-5.45 (m, 1 H);
13C NMR (CDC13), 131.0, 129.0, 39.6, 38.5, 32.4, 29.8, 28.8,

27.2, 26.2, 26.0, 22.5, 22.1, 20.1. The IR spectrum (film, KBr)
showed absorptions at: 2928, 2856, 1709, 1465, 1440 cm-1.


4.4.6.6-Tetramethyl-1,8-nonadiene-5-one (34). Diisopropylamine
(8.86, 0.0876 moles) and THF (80 mL) were allowed to stir to dry
ice/acetone temperatures under nitrogen in a 500 mL roundbottom
flask via an addition funnel. N-BuLi (43.8 mL, 0.0876 moles) in a
2.0 molar solution of hexanes was added dropwise via the addition
funnel maintaining the dry ice/acetone temperature after which
the addition funnel was rinsed well with hexanes. The resulting
lithium diisopropylamine (LDA) was then allowed to stir for an
additional 15 minutes. The addition funnel was then charged with
2,4-dimethyl-3-pentanone (10.0, 0.0876 moles) in a small amount
of THF which was then added slowly to the LDA solution. When the
addition was complete the mixture was stirred overnight at room
temperature. The solution was then cooled to 0C after which 3-
bromo-l-propene (10.6, 0.0876 moles) in a small amount of THF
was added dropwise to the enolate solution exothermicc) after
which the solution was allowed to stir at room temperature
overnight. The reaction was then quenched by the addition of H20
(100 mL) followed by diethyl ether (100 mL). The entire process
was then repeated for the second alkylation. The mixure was then
washed with water, 10% sodium thiosulfate, and finally brine. The
aqueous fractions should be re-extracted since there seems to be
significant product loss in the first set of washings after which the








ether fractions were dried over magnesium sulfate. The product
was purified yielding 34 as a colorless oil with the following
spectral properties: 1H NMR (CDC13), 1.18-1.25 (s, 6 H), 2.24-2.33
(d, 2 H), 4.92-5.06 (m, 2 H), 5.52-5.77 (m, 1 H); 13C NMR
(CDC13), 217.5, 135.0, 117.8, 49.1, 45.9, 25.8. The IR spectrum
(film, KBr) showed absorptions at: 2978, 1684, 1639, 1472 cm-1.
Mass spectrum: (El), m/e 194 (M+).


2.2.7.7-Tetramethyl-4-cycloheptene-l-one (36). In a drybox
equipped with nitrogen atmosphere la (0.020 g, 3.84 x 10-5
moles) was weighed into a Schlenk tube equipped with a stopcock
followed by 4,4,6,6-tetramethyl-1,8-nonadiene-5-one, 34 (2.0 g,
0.0103 moles). Rapid evolution of ethylene was evident and the
reaction was allowed to stir for one hour. The reaction vessel was
then closed off to the atmosphere, removed from the drybox, and
attached to a vacuum line where a static vacuum was applied and
the reaction mixture allowed to stir for an additional two hours.
The mixture was then vacuum transfer resulting in the isolation of
the cyclized product as colorless oil (1.7 g, 99 %) with the following
spectral properties: 1H NMR (CDC13), 1.08-1.13 (s, 6 H), 2.23-2.28
(d, 2 H), 5.68-5.75 (m, 1 H); 13 C NMR (CDC13) 218.6, 128.1,
48.9, 39.0, 27.5. Anal. Calcd. for Cl H180: C, 79.46; H, 10.91.
Found: C, 79.34; H, 10.87. Mass spectrum: (El), m/e 166 (M+).


1,11 Dimethyl-bicyclo-[9.4.11-13-hexadecene-16-one (37). In a
drybox equipped with nitrogen atmosphere la (0.020 g, 3.84 x 10-
5 moles) was weighed into a Schlenk tube equipped with a stopcock








followed by cis-2,12-(bis-3-propene)-2,12-dimethyl-cyclododecyl-
1-one, 35 (1.0 g, 3.4 x 10-3 moles). Rapid evolution of ethylene
was evident and the reaction was allowed to stir for one hour. The
reaction vessel was then closed off to the atmosphere, removed
from the drybox, and attached to a vacuum line where a static
vacuum was applied and the reaction mixture allowed to stir for an
additional two hours. The cyclized compound was purified by first
dissolving it in hexane followed by extraction with brine and
sodium carbonate solutions. Removal of the hexanes, resulted in the
isolation of the product as a colorless oil (0.89, 99 %) with the
following spectral properties: IH NMR (CDC13), 1.00-1.12 (s, 6 H),
1.15-1.50 (m, 18 H), 1.60-1.81 (m, 1 H), 2.04-2.10 (d, 1 H),
2.10-2.18 (d, 1 H), 2.42-2.48 (d, 1 H), 2.50-2.56 (d, 1 H), 5.86-
5.98 (t, 1 H); 13 C NMR (CDC13) 216.8, 130.4, 94.0, 54.2, 39.4,
38.4, 26.3, 26.1, 22.9, 20.3. The IR spectrum (neat, KBr) showed
absorptions at: 3340, 2900, 1683 cm-1. Mass spectrum: (EI), m/e
262 (M+).


1 -(2,2-Dimethyl-propane- 1-one)- 1 -methyl-3-cvclopentene (47).
In a drybox equipped with nitrogen atmosphere 4-(3-propane)-
2,2,4-trimethyl-6-heptene-3-one, 42. (0.50 g, 2.75 x 10-3 moles),
and catalyst la (0.01 g, 1.9 x 10-5 moles) were mixed together and
allowed to stir for three hours after which 1H NMR revealed both
starting material and cyclized product, 47. (60 % by 1H NMR), with
the following spectral properties: IH NMR (CDC13), 1.22-1.23 (s, 9
H), 1.25-1.26 (s, 3 H), 2.10-2.27 (m, 2 H), 2.85-3.10 (m, 2 H),
5.54-5.61 (m, 2 H). Mass spectrum: (EI), m/e 166 (M+).









1 -(2-Methyl-2-phenyl-propane- -one)- 1 -methyl-3-cyclopentene
(48). In a drybox equipped with nitrogen atmosphere 2,4-
dimethyl-2-phenyl-4-(3-propene)-6-heptene-3-one, 43 (0.30 g,
1.2 x 10-3 moles), and catalyst la (0.01 g, 1.9 x 10-5 moles) were
mixed together and allowed to stir for three hours after which 1H
NMR revealed both starting material and cyclized product, 48 (95
% by 1H NMR), with the following spectral properties: 1H NMR
(CDC13), 1.35-1.45 (s, 3 H), 2.30-2.50 (m, 2 H), 3.08-3.26 (m, 2
H), 5.70-5.81 (s, 2 H), 7.35-7.58 (m, 3 H), 7.80-7.92 (m, 2 H).
Mass spectrum: (El), m/e 216 (M+).


1.1-Dimethylester-3-cyclopentene (49). In a drybox equipped with
nitrogen atmosphere bis-(3-propenyl)-methyl-malonate, 44 (0.10
g, 1.9 x 10-5, and catalyst la (0.01 g, 1.9 x 10-5 moles) were
mixed together and allowed to stir for three hours after which 1H
NMR revealed only linear oligomers with the following spectral
properties: 1H NMR (d6-benzene), 3.10-3.28 (s, 3 H), 3.30-3.42 (s,
2 H), 5.37-5.49 (m, 1 H).


1-(2.2-Dimethyl-propane-1 -one)-1 -methyl-3-cyclohexene (50). In
a drybox equipped with nitrogen atmosphere 4-(3-propenyl)-2, 2,
4-trimethyl-7-octene-3-one, 45 (0.40 g, 2.04 x 10-3 moles), and
catalyst la (0.010 g, 1.9 x 10-5 moles) were mixed together and
allowed to stir for three hours after which 1H NMR revealed both
starting material and cyclized product, 50 (60 % by 1H NMR), with
the following spectral properties: 1H NMR (CDC13), 1.00-1.07 (d, 2







H), 1.10-1.18 (s, 3 H), 1.18-1.30 (s, 9 H), 1.90-2.10 (m, 4 H),
5.58-5.62 (t, 2 H). Mass spectrum: (EI), m/e 168 (M+).


1-(2.2-Dimethyl-propane-1 -one)- -methyl-4-cycloheptane(51 ). In
a drybox equipped with nitrogen atmosphere 5-(2,2-dimethyl-
propane-l-one)-l, 8-nonadiene, 46 (0.50 g, 2.25 x 10-5 moles),
and catalyst la (0.010 g, 1.9 x 10-5 moles) were mixed together
and allowed to stir for three hours after which 1H NMR revealed
both starting material and cyclized product, 51 (20 % by 1H NMR),
with the following spectral properties: 1H NMR (CDC13), 1.08-1.17
(s, 3 H), 1.18-1.24 (s, 9 H), 1.70-2.00 (m, 8 H), 5.58-5.62 (t, 2
H). Mass spectrum: (EI), m/e 194 (M+).











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87


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BIOGRAPHICAL SKETCH


Jasson Todd Patton was born on July 3, 1964, in Dunedin,
Florida. He began his undergraduate work in 1982 at Saint
Petersburg Junior College and then received his Bachelor of Science
degree in chemistry from the University of Florida in 1987. In the
fall of that same year, Jasson began graduate work at the
University of Florida, where he studied under Dr. W. M. Jones. He
received his Master of Science degree in 1989 in organometallic
chemistry. Jasson continued his graduate work in the fall of 1989
at the University of Florida, where he studied under Dr. K. B.
Wagener. He received his Ph.D. in polymer chemistry in 1992 and
began a career in industry with the Dow Chemical Company, in
Freeport, Texas.







I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.



Kenneth B. Wagenei, Chairman
Professor of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.



mes M. Boncella
Associate Professor of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.



Eric J. Enholm
Assistant Professor of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.



Kirk S. Schanze
Associate Professor of Chemistry







I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.



Alex E. Green
Graduate Research Professor of
Mechanical Engineering

This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences
and to the graduate school and was accepted as partial fulfillment
of the requirements for the degree of Doctor of Philosophy.


Dean, Graduate School


December 1992


























































UNIVERSITY OF FLORIDA


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