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Study of cyclocopolymerization

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Study of cyclocopolymerization
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Cyclocopolymerization, Study of
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Chu, Yuan Chieh, 1943-
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English
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xii, 127 leaves : ill. ; 28 cm.

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Absorption spectra ( jstor )
Anhydrides ( jstor )
Carbon ( jstor )
Copolymerization ( jstor )
Copolymers ( jstor )
Ethers ( jstor )
Isomers ( jstor )
Magnetic resonance spectroscopy ( jstor )
Monomers ( jstor )
Protons ( jstor )
Polymerization ( lcsh )
Polymers ( lcsh )
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bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

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Thesis--University of Florida.
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Includes bibliographical references (leaves 123-126).
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Typescript.
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Vita.
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by Yuan Chieh Chu.

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University of Florida
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STUDY OF CYCLOCOPOLYMERIZATION


by

YUAN CHIEH CHU















A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF

THE UII'.VEF::ITY OF FLORIDA IN PARTIAL FULFILLtIF1T OF THE

PE..UiIF rlENTS FOR THE r,'EFFEE OF DOCTOR OF PHILOSOPHY










UNIVERSITY OF FLORIDA

1977
































Dedicated to

the mother of Lawrence Chu


















ACKNOWLEDGEMENTS

The author would like to express his special gratefulness to

Professor George B. Butler for his encouragement and invaluable

guidance during the execution of this work.

The author also would like to express his appreciation to his

advisory committee and other faculty members in the Department of

Chemistry whose assistance and suggestions contributed much to this work.

He wishes to thank Mrs. Carol Albert for typing this thesis, Professor

G.B. Butler for checking the English composition, Dr. S.F. Tien for

his suggestions on the theoretical aspects, and T. Baugh for his work
13
on C nmr spectroscopy.

Finally, the author wishes to express great appreciation to his

wife, Rolan, whose forbearance and understanding made this work

possible.

The financial support for this work from the Department of

Chemistry and Professor G.B. -Butler's National Institutes of Health

grant is gratefully acknowledged.
















TABLE OF CONTENTS


ACKNOWLE ME1 T .

LIST OF TABLES .

LIST OF FIGURES .


ABSTRACT

CHAPTER


I. INTRODUCTION .


History of Cyclopolymerization and
Cyclocopolymerization .. 1

Mechanism of Cyclopolymerization .. 11

Mechanism of Cyclocopolymerization ... 16

Statement of Problem ... 22

II. THE STRUCTURE OF COPOLYMER OF DIVINYL ETHER-
MALEIC ANHi'L. FIDE SYSTEM 24

Introduction ... 24

Results and Discussion ... 25

The Mechanism of Cyclization ... 47

III. THE COPOLYMERIZATION OF DIVINYL ETHER-
FUMARONITRILE ... 52

Introduction ... 52

Results and Discussion ... 53

IV. EXPERIMENTAL . 100


Materials .

Equipment and Data .

Synthesis Related to Monomer Preparation

Copolymerization .


. 100

. 101

. 103

. 110


Page

. ii

. vi

. viii







Page

APPENDIX TEF E.LIHEMISTRY BACKGROUND FOR 5,5- AND
5,6-BICYCLIC SYSTEM IN THE COPOLYMER OF DVE-MAH ... .119

BIBLIOGRAPHY. . ... 123

BIOGRAPHICAL SKETCH . ... .. .127














LIST OF TABLES


Page

I. The Relation Between Concentration and Cyclization. 12

II. The Energetical Parameters for Cyclopolymerization. 15

III. The Reactivity Ratio of Copolymerization .. 18

IV. The Comparison Between JHD and JHH .. 28

V. The Chi-mi:cal Shifts for the Methine Protons of
DVE-MAH Copolymer .. 33

VI. Chemical Shift Differences Between cis and trans
Disubstituted Vicinyl Carbons in 13C nmr Spectra. 44

VII. Determination of Equilibrium Constant of FN-DVE in
Acetonitrile with Constant FN Concentration
(0.00101 m/l) .... 57

VIII. Comparison of Copolymer Initiated by Different Methods
in Acetonitrile. ... 61

IX. The Compositions of Copolymers Prepared in Aceto-
nitrile at Room Temperature within 10% Conversion 64

X. The Limiting Yield of Copolymerization with Excess
DVE in Feed Composition. 67
13
XI. Comparison of 1C nmr Spectra between Homopolymer of
DVE and the Copolymer of-DVE and FN ... 70

XII. The Light Intensity Dependence on Quantum Yield and
Rate in Acetonitrile at Room Temperature .. 73

XIII. The Linear Relations of Intensity (I) to the Quantum
Yields (4) and Rates 74

XIV. Comparison of Quantum Yield and Rate at 236 nm and
300 nm . ... 75

XV. The Rate of Copolymerization of DVE-FN System in
Acetonitrile at 300 nm, at I = 1.52 x 1016
Photons/Sec. . .. 82









Page

XVI. The Rate of Copolymerization of DVE-FN System in
Acetonitrile at 236 nm, at I = 6.4 x 1014
Photons/Sec. . .. 84

XVII. The Dependence of Total Concentration on Rate. .. 90

XVIII. The Determination of Reactivity Ratio rl ..... 97

XIX. The Copolymerization of DVE-FN System with Additives 111

XX. The Copolymerization of DVE-MAH System at Different
Temperature .... 116


vii















LIST OF FIC'FE[


Figure Page

1 IR spectrum of the copolymer of DVE-MAH prepared in
xylene at 1300C .... 29

2 60 MHz nuclear magnetic resonance spectra of (a) DVE-MAH
copolymer, (b) DDVE-MAH copolymer in acetone d 32

3 100 MHz nuclear magnetic resonance spectrum of DDVE-MAH
copolymer ....... ... ..... .35

4 300 MHz nuclear magnetic resonance spectra of (a) DVE-MAH
copolymer, (b) DVE-MAH [r ".H copolymer in acetone-d6 .. 36
13
5 C nuclear magnetic resonance spectra of (a) DVE-MAH
copolymer, (b) poly(maleic anhydride), (c) hydrolized
DVE-MAH copolymer . ... .40
13
6 C nuclear magnetic resonance spectrum of 2,3-dimethyl
succinic acid . ... 42
13
7 C nuclear magnetic resonance spectra of DVE-MAH
copolymer prepared at (a) 130, (b) 100, (c) 72, (d) 250C 46

8 The absorption of the complex of DVE-FN in acetonitrile
(a) 0.6 m/l of DVE, (b) 0.6 m/l of FN, (c) (DVE) =
(FN) = 0.6 m/1. . .. 54

9 The determination of the stoichiometry of the DVE-FN
complex in acetonitrile by continuous variation method
at 300 nm (DVE) + (FN) = 0.60 0.03 m/1. ... 55

10 Charge transfer absorption of DVE-FN complex in aceto-
nitrile. . ... ..... 58

11 IR spectra of the DVE-FN copolymer initiated (a) at
300 nm, (b) at 236 nm, (c) by Alb!:. ... 63

12 60 MHz nuclear magnetic resonance spectra of the DVE-FN
copolymer initiated (a) at 300 nm, (b) at 236 nm,
(c) by AIBN. . ... .. ... 63

13 The compositions of the DVE-FN copolymer initiated at
(a) 236 nm, (b) 300 nm. ..... 65


viii











13
14 1C nuclear magnetic resonance spectra of the copolymer
initiated (a) at 236 nm, (b) by AIBN, (c) at 300 nm. 69

15 The dependence f feed composition on rate at 300 nm
(I 1.52 x 10 photons/sec) for total concentration
(a) 2.40 m/l, (b) 1.20 m/l, (c) 0.60 m/1. ... 83

16 The depencenc4 of feed composition on rate at 236 nm
(I 6.4 x 10 photons/sec) for total concentration
(a) 2.0 m/l, (b) 0.6 m/1. ... 85

17 The dependence of total concentration on rate (x) at 300 nm,
fd = 0.5, (A) at 300 nm, fd = 0.6, (o) at 236 nm,
fd = 0.5, (*) at 236 nm, fd = 0.8. ... .' ..91

18 The determination of reactivity ratios -- (T) = 2.0 m/l,
at 300 nm ---- (T) = 2.0 m/l, at 236 nm, -- (T) =
1.1-4.5 m/l, with AIBN. . ... 98

19 60 IH:: nuclear magnetic resonance spectra of (a) DVE,
(b) DDVE with 250 ppm sweep width, (c) DDVE with 100 ppm
sweep width. . ... ... 105

20 60 MHz nucelar magnetic resonance spectra of (a) 2,2,2',2'-
tetradetueriodiethylene glycol, (b) diethylene glycol. 107

21 60 MHz nuclear magnetic resonance spectra of (a) bis-
(2-bromo-2,2-dideuterioethyl)ether, (b) bis(2-bromoethyl)-
ether. . ... ....... 109

22 The viscosities of the DVE-MAH copolymer in DMSO prepared
in (a) benzene at 76-780C with 77% conversion, (b) in
benzene at 51-540C with 25% conversion, (c) in benzene
at 61-640C with 47% conversion, (d) in CH.i at 60-610C
with 43% conversion, (e) in benzene at 28-2AOC with 31%
conversion initiated by light. .... .. 118


Figure


Page














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

STUDY OF CYCLOCOPOLYMERIZATION

By

Yuan Chieh Chu

June, 1977

Chairman: George B. Butler
Major Department: Chemistry

The well-known alternating 1:2 cyclocopolymer of divinyl ether

(DVE) and maleic anhydride (MAH) has been found to possess interest-

ing anti-tumor and biological activities. Recent research on the

structure of the cyclopolymer has raised a question about the ring

size of this cyclocopolymer. In this research program the structure

of this copolymer was reexamined by use of spectroscopic methods.

A linear, soluble copolymer was obtained by the copolymerization in

solvents with active hydrogens, such'as chloroform and xylene. The

ir spectra showed the existence of both monomers in the copolymer
-i
based on the strong bands at 1775, 1855, 1230 cm1 (cyclic anhydride),
-i
and 1090 cm- (cyclic ether).

By use of deuterated copolymers, the H-nmr peaks at 6 2.31, 3.47,

4.06, and 4.49 ppm with an area ratio of 2:1:1:1 were assigned for

the hydrogens of methylenes, methines on the backbone anhydride unit,

methines on the ring anhydride unit, and methines adjacent to oxygen

on the cyclic ether ring, respectively. Through the examination of








the possible isomeric structures of the bicyclic ring, the splitting

of each peak group was further assigned for cis and trans di-substi-

tutions on the anhydride unit.

The splitting pattern on the 300 MHz nmr spectrum of divinyl

ether 2,3-dideuteriomaleic anhydride copolymer confirmed the unsym-

metrical six-membered ring structure. 1C nmr spectra was discussed

and was consistent with the conclusion from the H-nmr spectra.

A chair-form six-membered ring with trans isomer next to each

side of the ring oxygen with a small portion of cis isomer was assigned

for the structure of DVE-MAH copolymer.
13
Based on little or no change of the 1C nmr spectra of the

copolymers prepared at different temperatures, it was concluded that

there was no significant change of structure caused by temperature

effect. This led to the sole assignment of the six-membered ring

structure of the copolymer as an energetically favored product.

A mechanism for the cyclization was proposed based on the HOMO-

LUMO interaction of the comonomers and the radical intramolecular

addition on the preoriented double bond. This mechanism led to the

formation of six-membered ring structure of the copolymerization as

the sole product.

The participation of the charge transfer complex in the cyclo-

copolymerization was investigated with the divinyl ether-fumaronitrile

system by light initiation. The evidence and the composition of the

complex were obtained by the UV spectroscopic method. The structure

of the copolymer was proposed on the basis of elemental analysis and
13
C nmr spectrum, as a mixture of 1:1 cyclocopolymer and 1:2 cyclo-

copolymer structures, both with six-membered rings. The initiation






mechanism involving polar deactivation of excited molecules and the

propagating mechanism were proposed to explain the rate maximum

phenomena and the relation between copolymerization rate and total

concentration of the comonomers at 236 nm and 300 nm irradiation.

A consistent result was obtained by the proposal of the participation

of the CTC in both the initiation and propagation processes.














CHAPTER I
INTRODUCTION

History of Cyclopolymerization and Cyclocopolymerization

It is well known that multifunctional monomers such as unconjugated

divinyl monomers are crosslinking agents in vinyl polymerizations.

However, certain compounds, such as diallyl phthalate and ethylene
2
diacrylate, undergo cyclization during polymerization, with the result

that 40-75% of the divinyl compound used is incapable of crosslinking.

Butler and coworkers3 found that several diallyl quarternary ammonium

salts polymerized to yield soluble and hence linear polymers containing

little or no residual unsaturation. Under the same conditions monoallyl

ammonium salts failed to polymerize. To explain the unusual results,

Butler and Ai4.1 o proposed an alternating intramolecular intermolecular

chain propagation mechanism to form a cyclic structure in the chain

(eq. 1). This type of process is now commonly termed cyclopolymerization.

Since these initial investigations, a large number of 1-6 non-

conjugated dienes of type I have been cyclopolymerized using appropriate

catalysis to yield soluble, most-ly saturated polymers with cyclic struc-

tures in the main chain.

In cyclocopolymerization, the comonomer contributes to formation of

the cyclic structure along with the nonconjugated diene. Butler reported

the first example of cyclocopolymerization. By copolymerizing divinyl

ether (DVE) and maleic anhydride (MAH), using a free radical initiator,

a soluble polymer was obtained. A mechanism similar to the cyclopolymer-

ization was proposed which is shown in equation 2.








This cyclocopolymer has been found to possess interesting


biological activity.


R


X


(Eq. 1)


X n+1


CH
X CH Si
2' /)
CH3



0
\ /
P 0 :S
/\ 0 / '
R


CH3
Ge

CH3





/So 2


S/R
/N










0 i"~


+ R* Initiation>
+ R -------;


0

o//
0


Intermolecular
propagation





Intramolecular
Cyclization







0



Intermolecular \t agation'





- Alte > >r
Alternate repetition


0


(Eq. 2)








The proposed mechanism was based on the following facts:6

(a) a soluble copolymer was formed, (b) little or no residual unsaturation

was detected in the copolymer and characteristic absorption bands for

cyclic anhydride and ether were observed in infrared spectra, (c) the

composition of the copolymer was close to a diene-olefin molar ratio

of 1:2 over a wide range of comonomer feed composition, (d) quantitative

conversion to copolymer was obtained, (e) the cleavage by hydriodic acid

and the incorporation of iodine into the copolymer indicated the pres-

ence of cyclic ether groups, and (f) neither monomer homopolymerizes

readily under the same condition as copolymerization.

Following Butler's discovery, the copolymerization reactions for

a wide variety of 1,4-dienes and olefins have been reported. Butler

and coworkers further studied some mono-olefin-1,4-diene systems to

produce 1:2 (1,4-diene:monoolefin) copolymer with generalized structure II.


Y CH
X X = 0, SO, Si

/ /2 / oCH3
Y n O0

y Y = -CN or Y-Y = 0

(II) "0


Stille and Thomson prepared, with a variety of free radical initia-

tors, a soluble copolymer of a nonconjugated diene, 1,5-hexadiene, and

sulfur dioxide. Elemental analysis of the copolymer samples substantiated

the existence of a material containing exactly two sulfur dioxide portions

to one of diolefin. The six-membered ring structure was confirmed by

comparing the ir spectra of the copolymer sample with pentamethylene

sulfone.





5





02 0

III



Price and coworker prepared the copolymers of N,N-divinyl

aniline with diethyl fumarate in bulk and solution with azobis-isobutyro-

nitrile (AIBN) at 600C. Diethyl fumarate, having widely different

polarity from that of divinyl aniline, and being reluctant to homo-

polymerize, polymerized with divinyl aniline in widely different monomer

concentration ratios to give copolymers of nearly constant 2:1 molar

ratio composition. The colubility of this copolymer and the negative

results of analysis for residual double bond by infrared absorption in

the 6.0-6.2 p region, supported the cyclic copolymer structure IV.


C 6H COOEt



S COOEt.
COOEt
COOEt

IV

The copolymerization of divinylphenylphosphine with acrylonitrile

was studied by Butler, et al. The copolymer produced was soluble in

DMF and showed no residual unsaturation. Elemental analysis indicated

the copolymer contained 0.265 mole fraction of divinylphenylphosphine

and 0.732 mole fraction of acrylonitrile. The structure of this

copolymer and the reaction for its formation are as follows (eq. 3):









CN
+C R-
+ nCH 2=CH -->


6H5

R-CH
'p ---------CH -CH --


.27 CN 0.73
S\CCN


CH
.6 5


CH2CH

CN
0.73


Rigid or multicyclic systems have been reported. Meyersen and

Wang0 prepared several copolymers of fused ring systems such as bicyclo-

pentene with sulfur dioxide or maleic anhydride in solution by free

radical initiation. Copolymer was obtained in the ratio of 1:2 as in

structure V in equation 4.


X = SO or
X :SO2 or


/.- /x

+ 2X~)

V n


K1>0


Eq. 4


Yamaguchi and Onoll reported the copolymerization of sulfur dioxide

and dicyclopentadiene (DCPD) in liquid sulfur dioxide with AIBN or other

radical initiators at o or 200C. Soluble copolymer was obtained with a

composition ratio of DCPD to sulfur dioxide of 1:2, and containing


C H5
6 5

^/ \ ^


0
2








virtually no residual double bond.

was proposed as VI.


The structure of this polysulphone


\ >-so,----

VI n
12
Butler and Pledger2 proposed 1:1 alternating copolymer of maleic anhydride

with 5-ethylidene-, 5-methylene-, and 5-vinyl-bicyclo(2,2,l)-2-heptene.

Evidence supported a tricyclic structure which incorporated maleic

anhydride as part of a six-membered ring repeating unit, for example

structure VII.


CHR


0 -0
Cx


The essential structure of the cyclocopolymers were proposed based

on the following methods.

1. Elementary analysis Most of the copolymers which have been studied

have a 1:1 or 1:2 comonomer composition in the copolymer regardless of

the wide range of feed composition, solvent, or initiator concentration.

2. Little or no residual absorption in carbon carbon double bond -

This indicates that all the double bonds in the diene were incorporated








into the copolymer. Only high degree of cyclization and crosslinking

can explain this observation. The residual unsaturation can be

detected by the absence of, or little ir absorption in the 6.0 to 6.2 p

region and nmr. Negative results of catalytic hydrogenation has been

used to show the absence of residual carbon carbon double bond in the

copolymer.

3. The solubility of copolymer and the absence of gelation at high

conversion rule out the crosslinked structure.

4. Existence of both monomers in the resulting polymer This can be

shown by the characteristic absorption bands of the comonomers in the
~--1
infrared spectra. For example, the 1100-1085 cm strong, broad band

for cyclic ether and the 1860, 1795 cm- bands for cyclic anhydride in

the ir spectra of DVE-MAH copolymers indicating the existence of both

comonomers in the copolymer.

5. The alternating ratios are always supported by elementary analysis.

Chemical method may support the proposed structure. Butler and

Guilbaultl3 hydrolyzed and dehydrohalogenated the copolymer of DVE-

chloromaleic anhydride, followed by the treatment with KMnO to get the

vic-diol copolymer. The degradation result of this vic-diol copolymer

upon periodic acid cleavage supported the 1:1 structure with only DVE

units on the backbone.



i. KOH 1. KMnO


SC1n 2. HC L H n 2.
V ---0 I
SCOOH

0
HIO
Eq. 5
H
COOH n C=O C=0
'H n COOH
COOH COOH








Both five- and six-membered rings can be formed during the cycliza-

tion step. Unfortunately not much work has been done along this line

to distinguish between these possibilities.

Stille and Thomson7 used the ir absorption spectra of model compounds,

VIII and IX, to compare with the 1,5-hexadiene-sulfur dioxide copolymer.

They concluded that the six-membered ring structure (III) was present in

the copolymer.








VIII IX



This method has also been used by Meyersen and Wang0 in their

fused ring system-sulfur dioxide copolymer as mentioned in the last

section.

Butler and Fujimori14 studied'ring size by the readiness of the dehy-

drohalogenation of the cyclocopolymer. The quantitative elimination

of only half the chlorine content of dichloro-maleic anhydride-DVE

cyclocopolymer provided the first support for the proposed six-membered

cyclic repeating unit. There would have been no such elimination if the

repeating unit were five-membered. If both the halogens and the

hydrogens at the 2-position to the oxygen were eliminated, the product

would be a furan derivative which should be detectable due to its

aromatic character.









aq. NaoH

O7 _-- -HC
Cl Cl n / n Eq. 6

O '\0 0 CO CO
Na Na




0

aq. NaOH i

0 0 n -.2HC I nN Eq. 7
COONa COONa




On the other hand, the ring structure of the cyclopolymer has been

intensively investigated by chemical and spectroscopic methods. Butler,

CrawshaS and Miller5 conclusively proved the existence of cyclic struc-

ture of cyclopolymer prepared by free radical initiation for diallyl

quaternary ammonium salts. A nondegraded polymer was obtained by

treatment with KMnO4. However, the ring size was not determined by

these authors. Later, by 13C nmr spectroscopy,6 both the five- and

six-membered rings were found in these cyclopolymers by comparing with

model compounds. Dehydrogenation of the cyclopolymer followed by the

identification of the resulting aromatic rings enabled Marvel and Vest17

to confirm the six-membered ring structure in the cyclopolymer of

2,6-dicarbomethoxy-l,6-heptadiene prepared by free radical initiation.
Me OMe Me
C OO 0e
C r R- KC10 Eq. 8
'n n








Spectroscopic methods have been applied to studying the ring
18
size for the cyclopolymer. Butler and Myers8 used both ir and nmr

spectroscopy to analyze the cyclopolymer obtained from dimethacrylamide

and its N-methyl and N-phenyl derivatives. They found that the polymers

were composed of both five- and six-membered rings. Electron spin
19 20
resonance studies have shown that the radicals from N-substituted

N,N-diallylamine in the presence of TiCl /H 02 or TiCl /N2NOH initiation

are five-membered ring cyclic species. It is possible that the radicals

involved in polymer formation have very short lifetimes (thereby not

detectable by ESR) and those radicals which are detectable are stable

but non-propagating species.

The extended chemical shift range, the absence of the simplicity
13
of proton decoupled 1C nmr spectra, in which each carbon resonates as a
13
singlet, makes the 13C nmr spectroscopy extensively useful for study of

polymer structures. Johns, Willing, Middleton,and Ong21 used the 13C

natural abundance pulsed Fourier transform nmr spectroscopy to distin-

guish the different structure features of the polymers formed by radical

induced cyclopolymerization of a series of N,N-diallyl amines by

comparing with the model compounds. The polymers of N,N-diallylamines

all contained cis and trans substituted pyrrolidine rings with the ratio

5:1. The polymers of N,N-bis(2-allyl)amine gave complex spectra due to

the presence of both cis and trans pyrrolidine and piperidiene rings.

Mechanisms of Cyclopolymerization

Since the discovery of cyclization in the cyclopolymerization, many

studies have been made on the nature of the cyclization step by theoreti-

cal consideration and experimental methods.








A statistical approach to cyclopolymerization was taken by Butler
22
and Raymond.22 They concluded that to explain the high degree of cycliza-

tion at high monomer concentration (Table I), a more favorable pathway

from 1,6-diene to cyclic polymer might exist than would be predicted

on a purely statistical basis.

Table I
The Relation Between Cyclization
and Concentration
Assumed
Monomer Cone. m/l Cyclization % Conc. m/1 Cyclization %

Diallyl quaternary pure
ammonium salts >5.0 96-100 monomer <50

Diallyl silanes 1.2-2.3 >95 1.00 70

Acrylic anhydride %8.0 9P-100 0.10 96

Diallyl phosphine bulk 100 0.001 100




Gibbs and Barton23 explained this by considering the presence of the

large pendant group which would tend to prevent intermolecular reaction

and will frequently be presented to the reactive species in a conforma-

tion which is favorable for polymerization (cyclization). Butler
24
et al. studied the effect of the stability of the cyclized radical on

the rate of cyclopolymerization. The overall rates of divinyl monomers

were considerably greater than that of the corresponding monovinyl

monomers, the ratios varying from 2 to 10. They estimated the effective

concentration of the intramolecular double bond with respect to the

radical propagation, and values greater than 20 M at 500C were obtained.

This incredible effective concentration indicated that a considerable

preorientation prior to reaction exists. This favorable preorientation

may be related to an electronic interaction between the developing








radical site and the intramolecular double bond or in the ground state

before the initiation as proposed by Butler.25

In an effort to explain the strong polymerization of 1,6-heptadienes

relative to their monoolefinic counterparts, Butler25 proposed that

an electronic interaction between the unconjugated double bonds of

1,6-dienes or between the intramolecular double bonds and the reactive

species after initiation might exist.




R *R





These interactions would reduce the entropy change in going from the

ground state to the activated state required for the intramolecular

pr.1.: .tion. The ground and activated state energies both would be

reduced. Mikulasova and Hvirik26 calculated the total activation energy

for radical polymerization of diallyldimethylsilane and found it to

be ca. 9 Kcal/(mole double bond) less than that for allyltrimethylsilane.

The electronic interaction is supported by UV absorption evidence,27

but it is not necessary for cyclopolymerization as shown by Gibbs.28

They found that in the case of methacrylic anhydride versus methacrylic

acid, there was essentially no difference in total activation energies

in the polymerizations. Marvel and Stille29 obtained a cyclic polymer

from 2,5-dimethyl-l,5-hexadiene, and suggested an unusual driving

force from diene monomer to cyclic polymer.

The activation energy for cyclization is not necessarily smaller

than the intermolecular addition for same radical as shown by several

authors based on the kinetic scheme developed by Mercier and Smets.30





14


They derived the kinetic relationships between intramolecular and

intermolecular propagation for the free radical polymerization of

acrylic anhydride.


(CH2=CHCO) 0
k0 1


(CH 2CHCO) 0

k.
1


0-


Eq. 9


The rate ratio of the intermolecular propagation (R.) to the intra-
1

molecular propagation (R ) was derived;
c


-E./RT
A.e i
R./R = 2 [monomer] l -
i c -E /RT
Ae c


where the difference in activation energies (E -E.) can be calculated.
c 1
Several E -E. values are listed in Table II. These results indicated
c i

that the intramolecular propagation step requires greater energies









than the intermolecular step (E >E.). However, the rate of cyclization
C i1

is considerably larger than for intermolecular propagation (k /k.>l).
C 1
The values for the ratio A /A. indicated a high entropy factor favoring
c 1

cyclization. The decrease in entropy for a cyclization step would

perhaps be expected to be smaller than that for addition of a new

monomer unit. Only rotational motion will be lost in cyclization; on

adding a new monomer molecule to the chain, the loss of translational

and rotational degrees of freedom will result. Therefore, as far as

entropy is important, cyclization would be favored over intermolecular

propagation.


Table II
The Energetic Parameters for Cyclopolymerization

Monomers E -E. Kcal/mole A /A. mole/l k /k. mole/l
C 1 c 1 c i

Acrylic anhydride 2.4 167 5.9

o-Divinyl benzene 1.9 50 2.8

Diallyl phthalate 0.3

Methacrylic anhydride 2.6 256 2.4




Guaita31 has studied the temperature independent factor of

cyclization parameters for the free radical copolymerization of acrylic

anhydride and divinyl ether. The results indicated that the high frac-

tions of cyclization in cyclopolymers from symmetrical unconjugated

dienes can be thermodynamically accounted for by an entropic effect

largely exceeding the energetical one. The entropy decrease was smaller

in the intramolecular reaction than in the intermolecular reactions.
25
These entropic effects are consistent with Butler's25 postulation of

the preorientation of two double bond by electronic interaction in both








ground and activated states. The nature of this preorientation between

the double bonds has been though to be due to a charge transfer complexa-

tion in the copolymerization, especially in the cyclocopolymerization to

produce alternating copolymers.

Mechanism of Cyclocopolymerization


Barton and Butler32 described a general

equation of 1,4-dienes and monoolefins where

is bimolecular in construction. The kinetic


in equation 10.

mi + M


m + M2




m3 M


kll
k11 .
-- m1
k12
-----> m3
m3
k
c
C
k33
---- il


copolymerization composition

the cyclic repeating unit

scheme considered is shown


k32
m + M ---2
3 2
k
kcl
m + M -----
c 1

k
Sc2
me + M2 -2

k21

m2 + M1 ---j
mS + M2


(Eq. 10)


M is the diene CH 2=CH-X-CH=CH2 where X is CH2, O, SO2, etc. M2 is

the monoolefin, CHY=CHZ. The m' is the radical,-QCH CHCHHCH2, m2 is the

radical --CHYCHZ, m3 is the uncyclized radical
3

Y/



Z

and m" is the cyclized radical
c


Y *




A five-membered ring structure for m" is possible.
c









The derived equation which related copolymer composition to monomer

feed composition in terms of five reactivity ratio parameters was given

as equation 11.
1 1 x
(1 + rx) + ( -)]
1 M a r
2 2


n = (E
1 x 3 1 r2 -
S[ + + 2] + + ( 1 + + )(1 + r x)
a r x M2 x c


where x = M /M2 is the mole fractional ratio of monomers in the feed,

n = m /m2 is the mole fractional ratio of monomers in the copolymer at

low conversion, rI = kll/kl2' r2 = k22/k21' r3 = k32/k31' rc = kcl/kc2'

and a = k /k32. The equation may be approximated to simpler forms in

the following cases.

a. If kc>>k32 so that a is very large and cyclization is the predominan

reaction of the radical, m3, the equation (11) gives
3'


n = (1 + rlx)(l + r x)/[r x + (r2/x) + 2]
1 c 2


q. 11)


t


(Eq. 12)


This is equivalent to considering the addition of monoolefin to diene

radicals to be a concerted bimolecular step proceeding through a cyclic

transition state and producing the cyclic repeating units.

b. If in addition there is a strong alternating tendency so that

r lr2,r =0 then equation (11) reduces in the limit to n= 1/2. This

predicts an alternating copolymer composition of 2:1 molar in contrast

to 1:1 for the similar limiting case of the classical binary copolymer
33, 34
composition equation and that for the cyclopolymer composition equation.3 34

c. If the diene has a negligible tendency to add to its own radicals and

rl=r c0 and there is also predominant cyclization, then equation (12)

gives


n = 1/[r,/x) + 2]


(Eq. 13)







32
All three cases have been found as in Table III.3



Table III
The Reactivity Ratio of Copolymerization

Case a Case b Case c

System r r2 r3 System System r2

DVE-AN 0.024 0.938 0.017 1,4-PD-MAH 1,4-PD-AN 1.13

DVS-AN 0.364 0.067 0.067 DVE-MAH DM-1,4-PD-AN 3.31

DVE-PMI DVE-4-VP 32.0

DVE = Divinyl ether; AN = Acrylonitrile; 1,4-PD = Dimethyl-l,4-penta-
diene; MAH = Maleic anhydride; PMI = N-Phenyl maleic imide;
4-VP = 4-Vinyl pyridine: DVS = Divinyl sulfone; DM-1,4-PD =
Dimethyl-1,4-pentadiene.


In cases (b) and (c) very low values for r have been reported.

This low value is remarkable in the case of monomers such as acryl-

nitrile, and indicates that almost all the AN radicals in m3 react

to form a ring. The actual ring formation may be either a stepwise

reaction or a concerted reaction to form the product. Orientation

of monomers via a charge transfer complex (CTC) prior to free radical

reaction explains this unusual cyclic structure and also accommodates

the kinetic data (eq. 14).



O R R "
.--- Concerted __

/ \0 n, (Eq. 14)


Stepwise


7








Evidence for the participation of a CTC in the copolymerization
35
between styrene and MAH was presented by Tsuchida and Tomono.3 They

concluded that the CTC and uncomplexed MAH took part in the copolymer-

zation. Evidence for participation of a CTC in the cyclocopolymeriza-

tion of 1,4-dienes with monoolefin was presented by Butler and Joyce36

on the comonomer pairs, DVE-MAH, DVE-MI, DVE-FN and dihydropyran

(DHP)-MAH. Butler and his group have intensively studied the partici-

pation of CTC in cyclocopolymerization. The evidence of the existence

of the CTC was confirmed by both UV and nmr spectroscopies. The

equilibrium constant of the complexation can be obtained by these

spectroscopic methods. The complex is formed by interaction of an

electron-rich donor (D) and an electron -deficient acceptor (A).


D + A ----- [D, A--]


The composition of all the complexes formed by 1,4-diene and monoolefins

were 1:1 complexes. The alternating copolymer compositions found were

2:1 in olefin to 1,4-diene ratio for most of the 1,4-dienes with MAH or

FN. This is consistent with the postulation that the CTC undergoes a

1:1 alternating copolymerization with the electron acceptors such as

MAH and FN, which can thus account for the structure of the copolymer.

Some 1:1 copolymer has been obtained which can be considered as the

product of the homopolymerization of the 1:1 complex.

One necessary requirement for these alternating copolymerizations

is that neither of the comonomers should be homopolymerizable to a

significant extent under the same condition of the copolymerization. If

the acceptor is homopolymerizable such as AN, MMA and 4-VP, acceptor will









be incorporated in the copolymer to a greater extent than the expected

value for 2:1 copolymer, i.e. 67%.

The contribution of complex can be further demonstrated by

terpolymerizations. The terpolymerization of styrene, MAH, and

2-chloroethyl vinyl ether (ChEVE) studied by Tsuchida and Tomono35

can be explained by treating the system as a copolymerization of two

complexes, styrene-MAH and ChEVE-MAH. Butler and Campus studied the

terpolymerization of DVE-MAH-AN system. The DVE-MAH ratio in the

terpolymer was always less than 1:1 and had a lower limit of 1:2

regardless of the feed ratio of the termonomers. These results were

interpreted in terms of the participation of the CTC of DVE-MAH in the

copolymerization process with either MAH or AN.

The MAH reacted with DVE in the absence of normal radical initia-
38
tion to form cyclic 2:1 copolymer.3 It was postulated that initiation

via a molecular complex occurred (eq. 15).



D A

D + A --- [D!, A7] D + A7 (Eq. 15)

D A

Active forms


The initiation of CTC can be demonstrated by photo-initiation of this
39 '
system and the DVE-FN system. Zeegers and Butler3 photo-initiated the

DVE-FN system with different wavelengths. They showed that both the

complex formed between DVE and FN and the noncomplexed species were

able to initiate the polymerization by light initiation.

Miller and Gilbert40 observed that vinylidine cyanide spontaneously

copolymerized with vinyl ethers when the two comonomers were mixed at








room temperature. Yang and Gaoni41 observed that 2,4,6-trinitrostyrene

as the acceptor monomer spontaneously copolymerized with 4-VP as the

donor monomer. Butler and Sharp42 reported the spontaneous copolymeriza-

tion of DVE and DVS.

The concerted cyclization has been argued by Butler and
13
Guilbault. They found that chloromaleic anhydride copolymerized

with DVE to form soluble copolymers of 1:1 composition with no residual

unsaturation. The ease with which the copolymer underwent dehydro-

halogenation indicated that the'hydrogen and chlorine atoms on the

anhydride unit are in a trans configuration as a result of a stepwise

cyclization process.

The steric effect of highly substituted acceptors, tetrahydro-

naphthoquinone (THNQ) and dimethyltetrahydronaphthoquinone (DMTHNQ) on

the copolymerization with DVE was studied by Fujimori and Butler.43

They found that the copolymers was in constant 1:1 composition regard-

less of the feed composition. A terpolymerization of these two acceptors

with DVE was studied. Both the copolymerization and terpolymerization

and the composition can be explained by assuming that competition

between an acceptor monomer and the CTC towards the cyclized DVE radical

in the propagation step appears to favor the CTC in CTC mechanism.

These authors4 studied the steric effect of substituted MAH on the

copolymerization with DVE. They found that (i) a strong complex gave

1:1 cyclocopolymer having a copolymer backbone consisting of only DVE

units, (ii) a sterically hindered acceptor would produce 1:1 cyclocopolvmer,

and (iii) a weak CTC and reactive acceptor would produce 1:2 cyclocopolymer.

They did not mention the reactivity change of the acceptor due to the

substitution. The alternating tendency and the rate increased by using









a large amount of ZnCl2 with the DVE-FN system. A 1:2 alternating

copolymer was obtained spontaneously. This system studied by Butler
44
and Fujimori was consistent with the participation of a CTC in the

copolymerization mechanism.
38
Solvent effects have been studied by Butler's group. The K

value (equilibrium constant of CTC formation) decreased with increase

of the dielectric constant of the solvent for MAH-DVE system. The

rate of the copolymerization and number average molecular weights

decreased in more polar solvents. In all cases, 2:1 copolymer resulted.
45
The study of the initial rate as a function of the feed composition

made it possible to determine the relative value of the different pro-

pagation reaction rate constants consistent with a mechanism by successive

and selective addition. However, participation of the CTC in a competing

mechanism with the above cannot be completely excluded.

In conclusion, a large portion of the evidence favors the partic-

ipation of CTC in both the initiation and the propagation steps in the

alternating cyclocopolymerization. A complete explanation or mechanism

to fit all known data has not been reported. It is reasonable to say

that the reactivity, the complexation and the steric hindrance of the

comonomers all take part in the alternating tendency, rate, and the ring

size in cyclocopolymerization. The solvent and initiator may also

determine the rate profile of this copolymerization.
Statement of Problem

The objective of the present research has been to study cyclo-

polymerization of donor 1,4-dienes with acceptor monoolefins and hope-

fully learn more about the role of charge transfer complex (CTC) formed

between the comonomers in the cyclocopolymerization mechanism and to








develop a method to elucidate the structure of the cyclocopolymer by

various nuclear megnetic resonance spectroscopic methods. The following

research was conducted with this purpose in mind.

The Structure Analysis of Cyclopolymer of Divinyl Ether-Maleic Anhydride
(DVE-MAH) Comonomer Pair.
13
The ir, H-nmr, and C nmr spectroscopies are employed for this well

known 1:2 alternating copolymer. The 100 MHz and 300 MHz H-nmr spectra

were investigated in order to analyze the ring size and hopefully the
13
cis and trans content of the bicyclic ring. The 1C nmr spectrometer

should give simpler spectra and by comparing with literature values,

it should be possible to determine the ring size of the copolymer.

A partially deuterated divinyl ether (DDVE) was prepared which should

simplify the H-nmr spectral analysis. The 100 MHz and 300 MHz H-nmr

spectra of this DDVE-MAH copolymer should give more information on the

copolymer structure and help in the assignment of the respective signals

of the spectra which has been shown to be informative based on the liter-

ature.16, 21
ature.

Rate Maximum Analysis

The study of the copolymer rate copolymerization rate as a function

of the feed composition made it possible to determine the participation

of CTC in the cyclocopolymerization. An irradiation at the wavelength

where only complex absorbed should confirm the initiation through CTC.

The participation of CTC in propagation can be supported by an analysis

of the proposed kinetic scheme. In order to compare the rate at the same

light intensity, the quantum yield was measured right after each irradia-

tion. The structure of the cyclocopolymer of divinyl ether-fumaronitrile
monomer pair was determined by elemental analysis and 13C nmr spectroscopy.
monomer pair was determined by elemental analysis and C nmr spectroscopy.














CHAPTER II
THE STRUCTURE OF COPOLYMER OF DIVINYL ETHER-MALEIC ANHYDRIDE SYSTEM

Introduction

The field of cyclopolymerization has been explored extensively. A

variety of monomers containing two isolated double bonds have been found

to polymerize to form linear polymers containing cyclic units and little

or no residual unsaturation. -High degrees of cyclization are obtained

when five- or six-membered rings can form and when all double bonds have
16
the same reactivity such as in diallylquaternary ammonium salts and
21
N-substituted diallylamines.21 The polymers of N,N-diallyl amines all

contained cis and trans-substituted pyrrolidine rings with ratio 5:1.

With a substituent on the 2-position such as N-methyl-N,N-bis(2-alkylallyl)-

amines, a complex spectra showed the presence of both pyrrolidine and
13
piperidine rings. The 1C nmr spectra of poly(diallyldimethylammonium)

chloride showed a predominant content of five-membered ring linked

mainly in a 3,4-cis configuration. Several works have studied the polymers

obtained from N-substituted dimethacrylamides.1' 4 In most cases five-

membered ring was found predominant with a small amount or no six-

membered ring.

The radical cyclization reaction involved in the polymerization has

been studied by means of model compounds. Julia reviewed the works

on the cyclization of the 5-unsaturated radicals.47 Without substitution

on the radical carbon, only five-membered ring product was obtained.

With electronegative substituents on the radical carbon, the six-

membered ring product predominated.

24








Smith studied the cyclization of several 2-(allyloxy)ethyl radicals
48
with tributyltin hydride. The 2-allyloxy ethyl radical gave the tetra-

hydrofuran derivative as the only cyclic product. The 2-methyl- and

2-phenyl-allyloxyethyl radicals cyclized to give both five- and six-

membered ring products; in the latter radical the pyran derivative was

the predominant product.

Smith also found that with higher temperature the percentage of the

unfavored product increased; this indicated that the ring formation is

temperature dependent. It can be concluded that a five-membered ring is

energetically favored in the case of symmetrical non-conjugated dienes.

A steric effect would change the direction for radical attack on the

double bond. For unsymmetrical non-conjugated dienes with opposite

polarization on each double bond, the six-membered ring is predominant

as explained later. A head to tail cross-propagation has been found for

several oppositely polarized vinyl monomer pairs, such as maleic anhydride-
49
vinyl ether pairs, which introduced an alternating copolymer. The

cyclocopolymerization of DVE-MAH is similar to unsymmetrical non-conjugated

dienes, in which the cyclization step involves a favorable cross-propaga-

tion reaction of oppositely polarized units.

It seemed worthwhile, therefore, to investigate the structure of the

copolymer of DVE-MAH and to study the temperature dependence of the five-

and six-membered ring distribution in the copolymer.

Results and Discussion

Synthesis and Copolymerization of Bis(2,2-dideuteriovinyl)ether

Due to the small amount of materials available, the structures of

the products in each synthesis step were determined by ir and nmr spectro-

scopy. A comparison of these spectra with spectra reported in the








literature and the spectra of the corresponding non-deuterated products

prepared by the same procedure confirmed the structures of the deuterated

compounds. In all cases the ir and nmr spectra of the non-deuterated

products were exactly the same as reported in the literature. Therefore,

the procedure for preparation of the non-deuterated ompounds were

applicable for the deuterated analogues.

A reaction scheme is shown in the following route:



SD H

O LiAlD /

THF AOH


DD


P D\ Br
/' \D KOH -D PBr3
0 -- 0 D 3
S D Triethanol ,D Pyridine
amine
D NBr
D





The 2,2,2',2'-tetradeuteriodiethylene glycol was prepared essentially

according to the method given by Bloomfield and Lee with only minor

modification.50 For complete reduction of anhydride, a prolonged reflux

period was required. In order to take the most advantage of lithium

aluminum tetradeuteride (LiAlD ), only a little excess of the deuteride

was used. The resulting glycol was soluble in water to a large extent,

hence, to isolate it from water solution was difficult. Even a salting

out process did not succeed. The reduction in ether solution was not








successful because of the low solubility of the anhydride. The reaction

seemed not to go at all. The best result was by using tetrahydrofuran

(THF) as solvent, with a small amount of water to destroy the aluminum

salt and release the glycol. The addition of 9 N sulfuric acid to dissolve

the aluminum salt did not improve the yield significantly. Therefore,

the complete dissolution of aluminum salt was not necessary. Water, fol-

lowed by dilute acid was used to bring the glycol into THF solution.

The addition of excess anhydrous potassium carbonate, K2C02, neutralized

the acid by evolution of carbon dioxide and absorbed water present in

the THF solution.

The diethylene glycol prepared by the same procedure showed exactly

the same ir and nmr spectra as reported in the literature. The ir

spectrum of 2,2,2',2'-tetradeuteriodiethylene glycol showeJ two
--1
absorptions at 2220 and 2110 cm of C-D stretching. The structure was

further confirmed by the nmr spectrum, in which a singlet was observed

instead of the multiple in the spectrum of non-deuterated diethylene

glycol. The peak ratio of 1:2 instead of 1:4 (for diethylene glycol) also

indicated that the product obtained was tetradeuteriodiethylene glycol.

The bromination of deuterated ethylene glycol was straightforward.51

The same method when applied to non-deuterated ethylene glycol gave a

product with exactly the same nmr and ir spectra as reported in the

literature. The ir spectrum of the resulting liquid for bis(2-bromo-
-I
2,2-dideuterioethyl)ether showed an absorption at 2170 cm which was

assigned to the C-D stretching. The nmr spectrum clearly confirmed the

structure with a singlet at 6 3.80 ppm. On the contrary, non-deuterated

dibromoethyl ether showed an AA'BB' multiple at 6 3.70 ppm.

Finally the synthesis of bis(2,2-dideuteriovinyl)ether was prepared

by dehydrobromination from the corresponding dibromo compound. Only








the nmr spectrum was analyzed. The disappearance of ABX system which

showed up in the spectrum of divinyl ether, was evidence of the replace-

ment of the four terminal hydrogens by deuteriums. A clear spectrum

was obtained by using larger sweepwidth. The constants for the hydrogen-

deuterium coupling (JHD) was obtained by analyzing this spectrum.

By multiplying JHD by 6.5, the corresponding hydrogen coupling constants
52
(JHH) were obtained and were found to be close to the reported value.
(Table IV).


Table(Table I).

Table IV

The Comparison Between JHD and JHH

Coupling J (Hz) Multiplied Reported
by 6.5 JHH (Hz)


trans 2 13.0 13.8

cis 1 6.5 6.2




The synthesized terminal deuterated divinyl ether (DDVE) was

copolymerized with MAH at 720C in cyclohexanone by AIBN initiation.

The polymeric product was isolated and purified as a white powdery

solid which was soluble in acetone and dimethyl sulfoxide.

A series of copolymers of DVE and MAH were prepared at different

temperatures. The ir and nmr spectra were obtained and are discussed in

the next section.

The Structure of Copolymer

Infrared (ir) spectra. The ir spectra were shown in Fig. 1. The
-i
two strong peaks at 1775 and 1855 cm1 correspond to the reported
-1 53
absorption of succinic anhydride at 1782 and 1865 cm for symmetric









































O
CO
Ln
-1




o















CD
C)
0o
-
0u








and antisymmetric carbonyl stretching, respectively. The strong peaks
-l
at 1230 and 950-920 cm were assigned for the C-O-C absorptions for
-i
cyclic anhydride unit. The strong peak at 1090 cm-1 with a shoulder
-l
between 1060-1020 cm was assigned for the C-O-C stretching for pyran

structure. The five-membered ring structure was ruled out by the fact
-1 54
that the C-O-C stretching absorption for tetrahydrofuran is at 1062 cm

The structure of the copolymer shown as structure X, with a 2,6-disubsti-

tuted tetrahydropyran ring and an anhydride unit on the 3,4-positions.






H H

H H
S H



0

X


The 1:2 composition of DVE to MAH has been reported by Butler based on

the facts discussed in Chapter I. The spectra for 2,5-disubstituted

tetrahydrofuran has been reported by Mihailovic,et al.5 They observed
-l
strong absorption at 1100 cm .for both cis and trans-2,5-dimethyl-

and diethyltetrahydrofuran.

The structure of the copolymer supported by ir spectra is likely

to have a six-membered ring. A conclusive result cannot be reached

because a suitable model compound for the comparison of ir spectra is

not available.

Hydrogen nuclear magnetic resonance (H-nmr) spectra.

The H-nmr spectra of polymers are usually broad. Therefore,








structure determination by H-nmr spectra is difficult. With the help

of the spectra of deuterated compounds and high resolution nmr spectro-

scopy, it is possible to simplify the spectra and separate the overlapping

peaks. The 60 MHz nmr spectrum for DVE-MAH system copolymer was shown

in Fig. 2a. A four peak pattern was observed at 6 4.49, 4.06, 3.47 and

2.31 ppm with an area ratio of 1:1:1:2. The H-nmr spectrum of the

copolymer prepared with DDVE and MAH under the same polymerization

conditions exhibited the disappearance of the strong peak at 6 2.31 ppm

(Fig. 2b). Only the weak peaks corresponding to the residual solvent

were observed. Hence, the peak in the spectrum of nondeuterated copolymer

at 6 2.31 ppm was assigned for methylene protons which were B to the

ring oxygen. It has been reported that in the spectrum of the copolymer

prepared with DVE-3,4-dideuteromaleic anhydride (DMAH), the two peaks

centered at 6 3.47 and 6 4.06 ppm disappeared.5 Hence, these two

peaks are due to the four methine protons linked on the anhydride forms.

The peak at lower field was assigned to the proton on the rir., based on

the fact that the proton in a fixed position within a bicyclic ring will

experience a downfield shift caused by the electronegative oxygen nearby.

The methine protons next to oxygen are expected to experience a

deshielding effect to shift tb lower field at 6 4.49 ppm. The methine

protons next to oxygen have been reported to absorb between 6 4.00 and
57
6 3.30 ppm.57 Strong electron withdrawing effect of the two succinic

anhydride groups apparently shifts the methine proton to even lower field.

According to this analysis based on peak assignment and area inter-

gration, it can be concluded that the repeating unit of the copolymer has

two to one ratio of maleic anhydride to DVE which are arranged in an

exactly alternating manner. A random distribution of bicyclic and succinic





32










I-w




w3






r0
00



0 0
E Qu

0D >










C+-
0
CT3
C, TJ
o0












0

0 c)
a~)

CD 0
Cd



Q) (












cr-

0
CD














br3



-H0
kO,-
0
S t
(\J
.0
-r1
















Table V

The Chemical Shifts for the Methine Protons of DVE-MAH Copolymer

Spectraa Next to 0 On the Ring On the Backbone
Anhydride Anhydride

60 MHzb 4.49 4.06 3.47

60 MHzc 4.38-4.44 4.08 3.50

100 MHzc 4.18-4.44 3.88 2.96, 3.30

300 MHzb 4.29, 4.57 3.92, 4.14 3.01, 3.30

300 MHzd 4.34, 4.46
4.67, 4.84

A6e 0.22 0.29-0.34

Af 0.28-0.47

All chemical shifts (6) are in terms of ppm relative to the
standard, TMS.
Non-deuterated copolymer.
cDeuterated copolymer of DDVE and MAH.
Deuterated copolymer of DVE and DMAH.


The chemical shift differences between the assigned cis and
trans methine protons.
See reference 59.








anhydride units would give a more complex spectrum than the one reported

here.

The 60 MHz H-nmr spectrum is not able to distinguish between the

five- and six-membered ring due to the broad peaks caused by vicinal

protons and the different conformations and configurations.

For the purpose of distinguishing the cis and trans disubstitutions

and the five- and six-membered ring structures, a high resolution 100 MHz

H-nmr spectrum was performed for the copolymer of DDVE-MAH in acetone-d6

at 500C (Fig. 3). The broad peak at 6 3.50 ppm with a shoulder at 6 3.16

ppm in 60 MHz spectrum was separated into peaks at 6 3.30 and 2.96 ppm.

The shoulder between 6 4.38 and 4.44 ppm was still unseparated and broad.

A 300 MHz nmr spectrum of DVE-MAH copolymer (Fig 4a) was performed by

Butler's group, in which a further separated pattern was observed.58

The three peaks for methine proton groups are summarized in Table V.

Bode and Brockmann reported that the cis- and trans-2,3-disubsti-

tuted succinic anhydride showed 0.47-0.28 ppm difference in chemical
59
shift and the difference decreased with larger substitution.59 Therefore,

we can assign the methine groups of highest field with 0.34-0.29 ppm

splitting as the anhydride unit in the copolymer backbone. The one at

the lower field with less splitting (0.22 ppm) is then assigned as the

anhydride unit on the ring, which is deshielded by the neighboring pyran-

oxygen as discussed in the last section. In disubstituted succinic

anhydride, the chemical shift for the trans form is less than that for

cis form, 6 >6 t thus the four peaks in the MHz spectra for anhydride
Scis trans'

protons can be assigned as: 3.01, 3.20, 3.92 and 4.14 for the protons on

trans-backbone, cis-backbone, trans-ring and cis-ring anhydride units,

respectively. On the backbone, the population of cis anhydride units



























0)

















0
o3 c a



















C))f


U
w0










S
2u5:













r r)
0 a
















C) U
0
oS u




a a
a










0









cn
rif
0~ 1/
0)
Sc)
25
0O
0~ 0 N

0L









bC













K-


OC
0
rC









O











0
'.r
E
a



o
m









o











o
mn


.0
a
0
C)




I
rcl







0


4-)







C)
a
o










Q)
()
n3













o '.
10
C4-)









E
CC





o










SC)
cd
00






.H H


SO
a
o0
o ct)





rW





a
E




0IR
Sl~
*3- Sr


9~~7-~:








and the trans anhydride units are more or less the same. In contrast, more

trans form was present in the ring. The latter can be explained by the

possible bicyclic ring conformation, where a trans configuration is more

favorable. Butler and Guilbault prepared the copolymer of chloromaleic

anhydride with DVE having cyclized 1:1 composition with only DVE units
13
in the backbone.3 They investigated dehydrohalogenation of the copolymer.

From the ease with which the copolymer underwent dehydrohalogenation, they

suggested that the hydrogen and chlorine atoms on the anhydride unit in

the ring were in a trans configuration. However, H-nmr spectra showed

the presence of both cis and trans conf1,irations with the latter in

favor.

By examination of the model of the bicyclic ring with large

substitutions on the carbons next to the oxygen, the six-membered ring

with chair form and trans junction is more favorable (trans isomer). In

this structure (XI), the two protons at the junction are in trans configura-

tion. A chair form with cis junction is another alternative configuration

(cis isomer). However, the latter configuration (XII) experiences more

ring strain. On the contrary, a bicyclic ring with two five-membered

rings experiences much strain and only cis junction is possible, especially

when one of the rings is an anhydride unit (XIII). The heat of combustion

of trans bicyclo(3.3.0)octane is greater than the cis isomer by ca.

6 Kcal/mole.6 [hu:., a trans junction pyran bicyclic structure with the

presence of cis isomer explains the analysis of 300 MHz nmr spectrum of

the DVE-MAH copolymer, based on the analysis of methine protons on the

anhydride units.

For a disbustituted cyclic ether, the chemical shift difference

between the cis and trans of the methine protons next to oxygen in the








literature have been reported to be between 0.11 and 0.51 ppm.6 62,

In the case of the DVE-MAH copolymer, the methine proton signal was

split into two peaks by 0.28 ppm as shown on the 300 MHz spectrum. It

is reasonable to assign this group of peaks as a mixture of the two

configurations with more trans-isomer present because of the larger

area in the higher field corresponding to the cis form which was more

populated for a favorable trans isomer.



H


0O


0

cis isomer 0 0
XII
H H
XIII






trans isomer
XI

This splitting pattern was more clearly observed in the 300 MHz

spectrum for the copolymer of DVE and DMAH (Fig. 4b). The two separated

methine proton (next to oxygen) peaks were further split into doublets.

The doublet indicated the nonequivalency of the two protons on each side

of the oxygen in the pyran ring. In contrast, the two protons for the

five-membered ring structure are more or less equivalent.

The methylene peaks on the higher field can be analyzed as a

mixture of two doublets; the larger doublet is assigned for trans isomer








which if further split by the fact that the methylene proton groups are not

equivalent. The splitting peak at the lower field with less intensity can

be assigned to the less populated cis isomer. In fused five-membered ring

structure, it is possible that the two methylene groups are linked in

either cis or trans configurations.63 However, a trans configuration

would introduce some strain in the bicyclic system with the two bulky sub-

stitutions on the pseudo equatorial positions of the half-chair conforma-
64
tion.6 A cis configuration with the possible conformation is shown in
64
structure XIII.64 In this structure both the two methine hydrogens and

the two methylene groups on the 2- and 5-position are equivalent. There-

fore, the splitting on Fig. 4b is most likely due to a chair form six-

membered ring with trans junction (trans isomer) with some cis isomer.

Further confirmation could be obtained by using bicyclic model compounds

and/or studying copolymers of additional monomers, e.g., CH2=CDOCD=CH2.
13
C3 Nmr Spectra

The line broadening inherent in H-nmr has severely limited the poten-

tial of this technique for polymer structure analysis. In contrast, the

extended chemical shift range, the absence of significant dipolar line
13
broadening and the simplicity of proton decoupled 1C nmr spectra, in

which each carbon resonates as a singlet, makes these spectra extremely

useful for the study of polymers.

The spectrum of the copolymer of DVE-MAH was shown in Fig. 5a.

The spectrum consists of five major peak groups. From comparison with

published data the following general assignments can be made: the broad

peaks centered at 6 31.4 ppm with a shoulder at 6 35.8 ppm for methylene

carbon, the broad peak centered at 6 44.2 and 51.5 ppm with a shoulder

at 6 53.7 ppm for the carbon adjacent to the carbonyl groups, broad peak















I,



/_~


3/











/703


o
C" ~


-------------
; 1 ^


(I)


CM

- C1
CM




-r


LC










co







E
a
&.


r:
\I/

Y
g,
u
/1\
r:


,0



r-l

0
o

o
0





>






00

0)

- )





o N
n3 >

O r-
0) 0

0






c0
4-)




icS
c I










bCm

*m 0
O0









centered at 6 78.7 ppm for methine carbon adjacent to the oxygen, the peaks

at 6 171.7 and 174.3 ppm for carbonyl carbons (Fig. 5a). The spectrum for

the copolymer hydrolyzed in D 0 does not change the pattern, but shifts

the peak to lower field (Fig. 5c). A comparison between the hydrolyzed

copolymer and the diacid model compound can be used for the assignment

of spectrum.

In a large series of compounds containing carbonyl groups, the

shielding is mainly influenced by the local electrons on the carbons.

The two carbonyl peaks Lui,.~-t that two types of carbonyl groups are

present corresponding to the two anhydride carbonyls proposed by H-nmr

apectra, where one of the anhydride units is in the backbone and the other

forms the bicyclic ring. The two carbonyl carbons in each anhydride unit

are not expected to be greatly different from each other as far as the local

electron density is concerned. Therefore, the broadening of the peaks can

be explained either by the two different carbonyl carbons in each anhydride

unit or by the mixing of both cis and trans anhydride forms. A broader

peak is observed at the lower field, which may indicate the equal mixing

of both the cis and trans forms.

The assignment of each carbonyl peak can be made by considering the

chemical shift difference between cis and trans configurations (A cis a),

which would broaden the carbonyl peaks. The carbonyl carbon absorptions

of succinic anhydrides have been reported to be between 6 171.7 and 175.3
65 13
ppm. The C nmr spectrum for a dl-meso mixture of 2,3-dimethyl succinic

acid is shown in Fig. 6. The chemical shift differences between the

two carbonyl carbons, the two methine carbons and the two methyl carbons

are 0.7, 0.9 and 1.4 ppm respectively. This small chemical shift differ-

ence for carbonyl carbons between the isomers of dimethyl succinic anhydride























CM








(J
C\J

OCM





r-3-


v


E-
0,
a




























co

t--


* '0
hCOr-A

bC *j
U~


cn~ 0
~d 0
C)








is expected for the carbonyl carbon peaks for the copolymer where only

a broadening effect is observed. The peak at the lowest field can be

thus assigned for the carbonyl carbons on the backbone because it is

broader than the other carbonyl carbon peak. This is reasonable because

the sharper peak then assigned for the anhydride on the ring, can be

explained by the less population of cis form. This sharper peak is

broadened by the hydrolysis of the copolymer as expected by the loss

of the rigidity of the bicyclic structure.

A comparison between the spectrum of the copolymer and poly(maleic

anhydride)(Fig. 5b)8 showed clearly that the broader carbonyl carbon peak

can be assigned to the anhydride unit on the backbone, and also, the methine

carbon peak at the higher field is for the anhydride unit on the backbone.

On the other hand, the two peaks at 51.5 and 53.7 ppm with a difference of

2.2 ppm can be assigned for the two non-equivalent methine carbons on the

six membered ring by comparing with the $- and y-carbons on the tetra-

hydropyran which has a difference of 2.8 ppm.

The peaks at the lower field of the methine carbon region (6 51.5-

55.5 ppm) are then assigned to the methine carbons on the ring anhydride

unit; the larger peak from trans isomer and the weak peak from the smaller

contribution of cis isomer. The methylene carbon peak is assigned to

the trans isomer which is broadened by the non-equivalency of the two

methylene groups in the copolymer. The shoulder at 6 35.8 ppm can be

assigned for the methylene carbons of the less populated cis isomer.

By comparing the methine carbons of the copolymer with poly-

(diallyldimethylammonium)chloride, (XIV), 1,1,3,5-tetramethylpiperidinium

iodide, (XV), and 1,1,3,4-tetramethylpyrrolidinium iodide, (XVI), in

Table VI, the chemical shift difference between the cis- and trans-

methine carbons in the copolymer is closer to the six-membered ring







structure than the five-membered ring structure.


P:
U &


Table VI

Chemical Shits Differences Between cis and trans Disubstituted
Vincinal Carbons in 13C nmr Spectra

Structure A6cis-trans (ppm)
On the Backbone On the Ring


Hydrolized
Copolymer
of DVE-MAH

2,3-Dimethyl
Succinic Acid

XIV

XV

XVI


0.9


4.5-5.0


1.8

6.2


66


Kunitake and Tsukino66 suggested an all five-membered ring structure

for the copolymer of DVE-MAH system by the fact that a highly symmetric

structure is involved, the two singlets observed for the carbonyl carbons


-'i


, b4










and the comparison of the estimated chemical shift values to the

experimental values. This suggestion can be argued against by (1)

in the spectrum of the copolymer, the difference between the two

carbonyl carbons in each anhydride unit is so small that a splitting

causes only the broadening of the peaks. Hence, the absence of the

doublet for each peak cannot be explained as the absence of the non-

equivalent carbonyl carbons, such as those in the six-membered ring

in the copolymer. (2) The analysis of H-nmr spectra was best represent-

ed by six-membered ring copolymer structure, although the unlikely

mixing of both five- and six-membered ring structures cannot be ruled

out completely.

The Temperature Dependence on the Copolymer Structure

Due to the possibility of the mixing of both six- and five-

membered ring structures in the copolymer, temperature effect experi-

ments were carried out to investigate the temperature dependence on the

contribution of these two structures.

The copolymers were prepared at different temperatures, 250, 720,

1000, and 1300C. The results are shown in the experimental section. The

spectra for each copolymer are shown in Fig. 7. No major change was

observed. The small side peak a.t 6 35.8 and 51.5 ppm both gradually

disappeared or flattened with the decreasing of temperature. This small

change cannot be considered to be real because of the accidental experi-

mental errors such as lower resolution and the different concentrations of

the samples. Even the different solvents used for preparation should be

considered.

It is reasonable to conclude that no significant change of structure

caused by the temperature effect is obtained. This fact can be explained











-co o---/- 0
H. H
A
/ H-CH CH

r\ 2









(b)











I






(d)


171.7 78.7 51.544.2 29.2
ppm (6)
Fig. 7 1C nuclear magnetic resonance spectra of DVE
MAH copolymer prepared at (a) 130, (b) 100, (c) 72,
(d) 25 OC









by the production of only one energetically favored product which is

the six-membered ring structure as revealed by all the spectroscopic

analysis.

The Mechanism of Cyclization

The structure and temperature analysis concluded that a highly

energetically favored six-membered ring copolymer was the product of

the copolymerization of DVE-MAH system. In cyclization of the sym-

metric non-conjugated dienes, the ring size is controlled by the

entropy effect of the two ring formation processes. A five-membered

ring product is favored because of the less entropy change involved.

With substitution, a sterically favored six-membered ring formation

is able to compete with the former process. Also, the substitution on

the radical carbon of the uncyclized radical makes both the processes

higher activiation energies and hence, less selective. At the extreme,

with two electronegative and steric substituents on the radical carbon,

a six-membered ring formation will be highly favored.47

The energetical factor is much different for a cyclization involving

non-symmetric non-conjugated dienes such as the cyclization in the

cyclocopolymerization of DVE-MAH system. During the cyclization step,

the vinyloxy double bond is attacked by a radical on the anhydride unit:


0.



0O
0 0



XVII / N'/-



0









This process can be shown to be highly enthalpy-controlled by

considering the closer energy gap between the HOMO of vinyloxy double

bond and the singly occupied molecular orbital (SOMO) of the anhydride

radical than that for the corresponding symmetrical diene cyclization.




LUMO


LUMO


SOMO
alkyl
radical SOMO
stabilized H':'lD
HOMO radical destablized
double double bond
bond


0




X- O




The HOMO of the vinyloxy double bond is polarized to have higher

orbital density on the terminal position.6 Therefore, a fast radical

addition on the terminal carbon of the double bond leads to a six-

membered ring radical. A copolymer with six-membered ring structure X

is thus obtained.

As discussed in chapter I, a charge transfer complex was proposed to

explain the fast cyclization. The charge transfer complex can be applied

here with the help of HOMO-LUMO concept to predict the ring structure

of the cyclization step.

The Milliken theory of overlapping and orientation principle predicts

that stabilization in the molecular complex formation should essentially








be determined by the overlap of the donor HOMO and the acceptor LUMO.68

In the examination of ir and Raman spectra of DVE, Claugue and Danti
69
proposed the presence of two rotational isomers.9 The more stable isomer

has C symmetry, in which the two vinyl groups, although coplanar are
s
non-equivalent. Hirose and Curl examined the microwave spectrum and
70
assigned the C conformer. They found a small nonplanarity caused

by H-H repulsion between the 3-hydrogen of the cis vinyl group and the

a-hydrogen of the trans vinyl group-(XVIII).


H






H
XVIII

cis-trans


The charge distributions in vinyl ether and vinyl methyl ether were

calculated by CNDO/2 method by Fueno, et al.67 It was found that a large

electron density was on the terminal position as in sturctures XIX and

XX.







O CH


XIX









This charge density of orbital actually describes the orbital density of

the HOMO of DVE. The LUMO of MAH has been described by Fukui as

structure XXI with higher orbital densities on the double bond carbons,

but antisymmetrical to the plane of symmetry of this compound.71

Therefore the most stable conformation for a DVE-MAH complex can

be expected as XXII, based on the conformer structure of DVE and the

molecular densities of both.comonomers.


XXI
0 path a


R, 0


R* path b



R


XXII


(Eq. 16)




XVII


.ii-n this complex is initiated by a radical, a six-membered ring

radical will be formed concerted (Path a) or stepwise through an anhydride

radical addition on the terminal carbon of the vinyloxy unit (path b).

This complexation would reduce the energy gap between the complex and

the propagating anhydride radical, thus, a radical addition on the

complex occurred and the reaction is supposed to be fast. This special









complexation and/or interaction would significantly reduce the activa-

tion enthalpy for the formation of six-membered ring. In the range

of the temperature sutdied, a five-membered ring formation cannot compete

with it at all, which explains the temperature independence on the

structure of the cyclocopolymerization.

In conclusion, on the mechanism of the cyclization and copolymer-

ization of DVE-MAH system, it is reasonable to be stated as follows.

(1) The intramolecular cyclization is favored over the intermolecular

addition due to the lower entropy change of the former process than the

latter one. This explains the high degree of cyclization.

(2) The entropy preference cannot be explained on the base of activation

energies and the statistical probability. A preorientation either

through the delocalization of the radical with the intramolecular double

bond or the formation of complex is proposed.

(3) This preorientation would lead to a six-membered ring structure

by a favorable energy factor based on the !IlH',) orbital density of DVE.

For a symmetrical nonconjugated diene the five-membered ring cyclization

is favored by the entropy factor.

(4) A faster rate of this cyclocopolymerization than the copolymerization

of the corresponding monoolefin -pairs can be explained by the closer

energy of the anhydride radical to the complex.

The proposed cyclization mechanism can be applied on other comonomer

pairs and is worthy of further investigation.















CHAPTER III
THE COPOLYMERIZATION OF DIVINYL ETHER-FUMARONITRILE

Introduction

It was pointed out in Chapter 1 that a donor-acceptor pair of

comonomers could produce alternating copolymer through a charge transfer

complex (CTC). In the cyclocopolymerization of donor 1,4-dienes with

acceptor monoolefins, alternating cyclocopolymers having 1:2 composi-

tion were obtained for several systems. The participation of CTC formed

between the donor and acceptor was proposed to explain the alternating

copolymerization. However, it has been known for sometime that the

compositions for the copolymers are 1:2 while the stoichiometry of the

CTC are always 1:1. An alternating copolymerization of a CTC and a free

monoolefin was proposed as an explanation. It has been shown that

when an acceptor monoolefin is highly sterically hindered and hence much

less reactive, according to the above explanation, a 1:1 cyclocopolymer
14, 43
was obtained apparently through the homopolymerization of CTC., 43

With a less sterically hindered monoolefin and less reactive monoolefin

it is possible to form a cyclocopolymer with composition between 1:1

and 1:2. The cyclocopolymer of DVE-FN has been reported having the FN

content between 0.55 and 0.63 mole fraction which is in the range of
32
0.50-0.67 for the 1:1 and 1:2 composition.32 With dilution, less FN

content was reported and a contribution of either homopolymer structure

of DVE and/or 1:1 comonomer unit in addition to the regular 1:2

comnomer unit was proposed as an explanation.37
comonomer unit was proposed as an explanation.









A further structural analysis and the study of the participation of

CTC in the copolymerization are discussed in this chapter

Results and Discussion

Study of the DVE-FN complex in Acetonitrile

On the basis that the complex formed between DVE and FN may

participate in the mechanism of initiation of the photocopolymerization

in acetonitrile solution, the characteristics of the complex were

studied in the same solvent. The existence of the complex was estab-

lished by UV spectrophotometry. A mixture of 0.6 m/l of DVE and 0.6 m/1

of FN showed a large absorption between 250 nm and 350 nm (Fig. 8)

although a distinguishable new absorption band was not observed.

This large enhancement of absorption indicated the presence of complex.

A 1:1 stoichiometry was determined by the continuous variation method
72
at 300 nm- (Fig. 9). The maximum of the absorption for different

compositions of DVE and FN, while their total concentration was kept

constant was found for equimolar composition.

The charge transfer complex of an acceptor-donor pair is in

equilibrium with the free components. The charge transfer complex exists

in resonance between the no-bond state and the dative state; thus the

wave function of the charge'transfer complex (TCT) can be expressed as a

linear combination of wave functions of the no bond state [Y(D,A)] and

the dative [W(A*, DT)] (Equation 1 and 2).


K
c (
A + D --- [(A,D) + (A*, D.)] (Eq. 17)


CT = a'-(A,D) + b.'(A7 DI)


(Eq. 18)
























o c

oyr,






S0 o
m 00


oo


C)
O 11











4 0
*H r










N *H-





0 *r-Q





-0 0
-P



















CDM
0o o
- O >J o
xC D










oo


So Qo




CM O


CD;


a









I -IA0























































































i O O o 0
aoueqjosqv


0*





C+
C X II










o 4-











-H 4 -)
Eo











,r-i
,O







4-) 0
0
co
0 a
O










0 --


a)
S0o3


0 4

*H 4.o
m r'- o

o o
-o CD









C *H)


0
o oO











4) C
u








F Iol





p-i (ti








For a regular loose complex, a2>>b2 in the ground state of the com-

plex. The dative structure corresponds to an ionic-radical-like pair.

There must be also an excited state (41CT) which can be called a charge
73
transfer state given by


CT = b o'(A,D) + a Y,(AD,D*) (Eq. 19)

;':2 '2
The excited state is mostly dative (a 2>>b ); excitation of an electron

from TCT to 'CT essentially amounts to the transfer of an electron from

donor to acceptor. Spectroscopic absorption would occur with this excita-

tion (charge transfer absorption). A charge transfer absorption is

possible for any pair of molecules if in contact, even if they do not

form a stable complex.

A complete absorption spectrum of a complex consists of absorption

to (1) locally excited state (states of donor or of acceptor, more or

less but usually not greatly modified in the complex.) (2) charge

transfer states [(YCT in Eq. 19, and other charge transfer states includ-

ing the excited dative structures, for example 4(D* ,A*)].

The equilibrium constant (K ) of the complex can be measured by

using Merrifield and Phillips method.74

Ac
(D) -K A + K (A)c (Eq. 20)
(D)o c Ac c ( Ac

(D)o = The initial donor concentration

(A)o = The initial acceptor concentration

Ac = Absorbance of complex at certain wavelength

K = The equilibrium constant for the formation of weak complex

=(Complex)/(D)(A)










hc = The extinction coefficient of the complex at wavelength.


For a series of solutions containing different concentrations of

DVE but with constant concentration of FN, with condition (DVE)>>(FN),

a plot Ac/(DVE) against Ac should be linear. From the gradient of the

line, K may be evaluated directly without recourse to an extrapolated

intercept. The absorption of DVE-FN complex and the resulting plot in

acetonitrile are shown in Fig. 10 and Table VII. The equilibrium con-

stant was small (K = 0.10) and cannot be evaluated exactly, but it is

compatible with the equilibrium constant measured in methanol solution
39
(K = 0.12 to 0.20).
c



Table VII

Determination of Equilibrium Constant of rEN-DVE in
Acetonitrile with Constant FN Concentration (0.00101 m/1)

(D)0 280 nm 300 nm

m/c A A/(D)0 A A/(D)0


0.846 0.031 0.0520 0.013 0.0154

1.69 0.081 0.0479 0.029 0.0172

2.12 0.100 0.0472 0.031 0.0146

2.96 0.137 0.0463 0.042 0.0142

3.81 0.152 0.0399 0.040 0.0105

K 0.09 0.11
c




The equilibrium constant of complexation can be determined by nmr
75
spectroscopy using the Hanna-Ashbaugh equation.75 The attempted nmr

method failed because one of the quartet absorptions of the a-vinyl






















































































L_ (NJ CH

0 C C C) C

ao-qoq


()
H


4-)
rl

0
cj C)
Q)
0 0










0




4-)





0)

0 ) 0




0
co









(,0








Ct



C')
Q 0)









*rl









proton of DVE covered the peak of the protons of FN, whose chemical shift

was to be used to determine the equilibrium constant in acetonitrile.

The Structure of the Complex

The spectroscopic determination of stoichiometry and the equilibrium

constant of the charge transfer complexes of monoolefins with 1,4-dienes
37
have been thoroughly discussed previously.37 'i lr ly, in all cases

studied the stoichiometry is 1:1. The structure of the complex has not

been established. Either one or both of the double bonds of the 1,4-diene

can be completed with acceptor. Take DVE and FN as an example:


0 0


A, / 1:1 complex
CN CN
C-N, CN CN -- -CN






The first structure is not likely because with a free double bond

available, a second acceptor would be completed more or less as easily

as the first acceptor molecule to form a 1:2 complex.


S70 CN
CN 1:2 complex


CNCN

As pointed out in Chapter II, considering the conformation of DVE

and the orbital densities of both HOMO of DVE and LUMO of acceptor, the

most stable conformation of the complex can be predicted as structure X:III.

The proposed relation between no bond state and the dative state of this

complex is shown in equation 21.











NC



t N

9 XXIII





NC
NC

.--/-N "(Eq. 21)

+ 0 __
Dative state No bond state


At ground state the complex can be represented by the no bond state,

the excited state (CTC)* after the absorption of appropriate light energy,

can be represented by dative state. In general an excited state would be

radiationlessly deactivated without associating with external environment.

In the case of (CTC)*, the state is so polar that the environmental polar

molecules (acceptor, donor and ground state complex) would participate in

its deactivation processes.

At 236 nm, while most of the light is absorbed by the free monomers

to form excited monomers, the excited state of DVE would interact with

the ground state of FN to form an exciplex which possesses higher energy

than the previously mentioned c rge transfer state [(CTC)* formed by

irradiation at 300 nm where only the complex absorbs].76 The exciplex is

polar enough to be deactivated with the participation of ground state

molecules. (Scheme I)











300 nm environmental
(DVE -- FN) -- -- (DVE -- FN)* en DVE + FN
molecules


236 nm FN environmental
DVE n DVE* -F-- (DVE**FN) Dr -ome DVE + FN
molecules


environmental
molecules



DVE



Scheme I



The Structure of the Copolymer of DVE-FN System
13
Ir and H-nmr spectra. The ir, H-nmr and 1C nmr spectra were record-

ed for the copolymers prepared by irradiation at 300 nm, 236 nm and with

AIBN, in acetonitrile with feed composition fd = 0.5 (Table VIII).



Table VIII

Comparison of Copolymers Initiated by Different
Methods in Acetonitrile

Feed Composition Initiation Conversion md'

(FN) (DVE)

0.6 m/1 0.6 m/1 AIBN 44% 0.408

0.6 m/1 0.6 m/l 236 nm 40% 0.402

0.6 m/1 0.6 m/1 300 nm 55% 0.486
*Molar fraction of DVE in copolymer calculated from nitrogen
and carbon content





62


All the copolymers showed the same characteristics in ir and H-nmr

spectra, thus indicating that the same propagation processes are employed

for all methods of initiation.
-I
The copolymers absorbed in the infrared region: 2250 cm- (s)

(CN stretching) and near 1100 cm-1 (broad)(ether group), showing the

existence of the comonomer units. There was also the presence of
-1 3
vinyloxy double bond absorption at 1630 cm It has been observed32

that only a small amount of residual unsaturation (from 2.0 to 3.5%) was

in the copolymer prepared by the initiation of AIBN in dimethylformamide.

The infrared spectra of copolymers initiated by light at both 236 nm

and 300 nm had the same characteristics as the one initiated by AIBN in

acetonitrile (Fig. 11). It is reasonable to assume that the same small

amount of unsaturation was in the photocopolymers. This conclusion was

also shown in the H-nmr spectra (Fig. 12) where no absorption contributed

by vinyloxy double bond was observed. Therefore, there is no significant

contribution of the structures with the pendant vinyl group in the copoly-

mer.





0

/ XXIV

\ CN / n

CN

The composition of the copolymer. The composition of the copolymers

has been determined over a wide range of monomer feed compositions. The

copolymers of DVE-FN are quite hygroscopic. The elemental analysis showed

higher hydrogen and oxygen weight p-r>c:nrtjr, than calculated from nitrogen





























Wave number (cm- )
Fig. 11 IR spectra of the DVE-FN copolymer initiated
(a) at 300 nm, (b) at 236 nm, (c) by AIBN.


ZY VdN
CN
CN

a








7.0 6.0 5.0 4.0 3.0 2.0 l.O 0
ppm (6)
Fig. 12 60 MHz nuclear magnetic resonance
spectra of the DVE-FN copolymer initiated
(a) at 300 nm, (b) at 236 nm, (c) by AIBN


~ I







and carbon. The nitrogen content is only from FN monomer, the calculation

of the number of nitrogen atoms permitted the determination of the

copolymer composition.



no. of moles of FN = no. of moles of nitrogen atoms/2



Sno. of moles of carbon atoms no. of moles
no. of moles of DVE = o F
of FN x 4






md = the molar fraction of DVE in the copolymer



no. of moles of FN
no. of moles of DVE + no. of moles of FN


The results are shown in Table IX and Fig. 13.


Table IX

The Compositions of Copolymers Prepared in Acetonitrile at
Room Temperature within 10% Conversion

Concentration (m/l) 300 mn 236 nm
b c
(FN) (DVE) fd md m

0.4 1.6 0.80 0.410 0.408

0.8 1.2 0.60 0.372 0.436

0.6 0.6 0.50 0.486a 0.402a

1.2 0.8 0.40 0.412 0.400

1.6 0.4 0.20 0.351 0.436

Average 0.406 0.416

More than 40% conversion.
Molar fraction of DVE in feed.
Molar fraction of DVE in copolymer calculated from
nitrogen and carbon weight percentage.








































ol x


0


K
\ \
Ctd\ *0\


\\ \


I I I


-= --


I I

o o
0 0


0 0 0 0


io od
-P
4.)


0

4()
co 4
Or





0o
E)
4-1

o 0
0
o












o
0 ,(


















C
oo


o o
o
E ^








c'3
bt )'>








There was no apparent trend for compositions of copolymer. The

copolymers irradiated at different wavelengths have similar compositions

(average md = 0.406-0.416). It indicated that the same propagation process

was employed for both wavelengths. For a typical 1:2 copolymer and a 1:1

copolymer, md is 0.33 and 0.50 respectively. The compositions of both

copolymers fell in the range from 0.351 to 0.486 within a wide range of

feed compositions. Together with the spectroscopic data this is the basis

of assuming a copolymer containing both the 1:1 and 1:2 copolymer structures

XXIV. Note that is is not necessarily a block copolymer in the sense of

1:1 and 1:2 monomer combinations. The 1:1 repeating unit has been found
77
in the copolymerization of p-dioxene-MAH,77 DVE-DMTHNQ and DVE-THNQ
43
systems, in which the homopolymerization of a 1:1 CTC was considered.

CN

0 "0


CN XXV
S CN x
CN CN



When the reaction time of copolymerization was long enough so that

the reaction was almost completed, it was observed that the yield at 236 nm

for large excess of DVE in feed composition was more than the corresponding

theoretical maximum of conversion of a perfect 1:2 copolymer but less than

or close to the 1:1 copolymer (Table X). At 300 nm the yield was less

than the theoretical 1:2 copolymer.

The excess yield at 236 nm can be explained by the involvement of

either the homopolymerized DVE or the 1:1 copolymer structure in the 1:2

overall copolymer structure. When FN is about used up at the end of the










reaction, homopolymerization of DVE has a chance to compete with the

copolymerization. The fraction of DVE in copolymer (md) supports the

involvement of homopolymerization of DVE. What is important is that the

close value of nd at both 300 nm and 236 nm (md = 0.560.03) indicating

that the involvement of homopolymerization is in the propagation process

instead of the initiation process, in other words, in the early stage

of the copolymerization, the homopolymerization is not involved.



Table X

The Limiting Yield of Copolymerization with
Excess DVE in Feed Composition


Wavelength
(nm)

300






236


Feed
Composition


2

5

10

1

2

5

10


Yield
(mg)

24.8

40.1

115.7

25.7

45.1

78.9

16&.0


Theoretical Yield
1:2 Copolymer 1:1

32.5

49.7

135.1

24.8

32.5

57.3

143.7 1


The fraction of DVE in copolymer calculated from nitrogen and carbon
content.
Based on the reacted amount of FN.
Average = 0.56.





The different initiating wavelength would finally form the same

intermediate or intermediates which initiates the same propagating radicals.

13
The structure of this copolymer can be further confirmed by 1C nmr spectro-

scopy.


b
(mg)b
Copolymer


a, c
md


32.5

42.5

75.0

.88.2


0.54

0.59



0.52

0.57








13 13
The 1C nmr spectra. The 1C nmr spectrum of the copolymer is

shown in Fig. 14. The four peaks at 6 118.5, 117.9, 116.6, and 116.1

ppm from TMS in the CN region supports the six-membered ring structure

where two of them correspond to the two unsymmetrical CN's on the ring

and the other two correspond to the CN's on the skeleton.

It was pointed out in Chapter II that the small difference between

the two carbonyl carbons would only cause a broadening of the peak

instead of splitting it. This assumption can be applied here that the

doublet of each CN peak does not indicate two non-equivalent CN's in

the ring or on the backbone. The chemical shift difference (0.5-0.6 ppm)

between each peak in the doublet is close to the difference of the carbonyl

peaks of dl-meso mixture of 2,3-dimethyl succinic acid (0.9 ppm). We

can assign the doublet as the consequence of the mixture of cis- and trans-

dicyano substitutions on each fumaronitrile unit. These assignments will

lead to a reasonable conclusion that in backbone, cis- and trans-disubstitu-

tions are more or less equally populated, by considering the equal

intensities of the doublets as shown on the peaks at 6 117.9 and 118.5 ppm.

The CN's at 6 116.6 and 116.1 ppm indicated the different populations of

cis- and trans-disubstitutions, whichare possible during the ring formation.

It is difficult to assign the chemical chifts of the CN groups

without comparing with model compounds, but at least a copolymer with

the 1:1 and 1:2 copolymer composition is consistent with the spectra.

The two C-O-C peaks in the C-O-C region indicated the existence of
13
two different C-O-C linkages in the copolymer. Comparing the 1C nmr

spectra of homopolymers of DVE with the copolymers enabled us to clarify

e exclusion of homopolymer structure in the copolyr.78 (Table XI)
the exclusion of homopolymer structure in the copolymer. (Table XI)















































Fig. 14 13C nuclear magnetic resonance
spectra of the copolymer initiated (a) at
236 nm, (b) by AIBN, (c) at 300 nm.









Table XI


Comparison


13
of 1C nmr Spectra Between
the Copolymer of DVE


Homopolymer of DVE and
and FN


Chemical Shift
(ppm from TMS)
of C*'s


No. of CN Substitutions
on C*'s


Calculated
total shift
(ppm)


Homopolymer


a, 0; B, 1; Y, 2

a, 0; l, 1; Y, 1


*The special carbon in consideration.


XXIX


XXVI


CN CN
CN CN


Material


XXVIII

XXIX

XXX


82.3, 83.4, 151.1

84.2

77.8


Copolymer


XXVI

XXVII


79.6

76.7


XXVIII


XXVII








Comparing the C*'s in trimethyleneglycol (two oxygens are three carbons

apart) with pentamethyleneglycol (two oxygens are five carbons apart),

there is a 2.9 ppm difference in chemical shift due to the distance of
79
the two oxygens.79 The 2.9 ppm difference of the two C-O-C absorption

in the copolymer can then be explained by comparison between the C*'s

in structure XXVII and then XXVI.




HO OH HO OH



59.2 ppm 62.1 ppm







In conclusion, at low conversion, the copolymer contained a mixture

of structures XXVI and XXVII, a small amount of residual unsaturation and

probably some homopolymer structure which can be neglected for kinetic

consideration. The average md = 0.41 corresponding to a %". of structure

XXVII. This ratio of structure XXVI to structure X'".'11 was reflected
13
by the almost equal intensity of the two C-O-C absorption in 1C nmr

spectra.

To distinguish between pure five- and six-membered ring structures

is very difficult because of the lack of information. As discussed

in Chapter II, it is unlikely to have a mixture of both six- and five-

membered rings structures in the copolymer because of the simplicity of

the spectrum. Furthermore, a favorable conformation of the complex and

the orientation of the cyclization makes the six-membered ring structure

more possible.









Quantum Yield Study

Quantum yields for formation of copolymer were measured in aceto-

nitrile and at different wavelengths. The intensities are different at

different wavelengths for monochromatic light source. It will be pos-

sible to compare the quantum yields at different wavelengths by knowing

the dependence of intensity on quantum yield.

The data obtained for 0.6 m/l FN and 0.6 m/l DVE in acetonitrile

at-300 nm showed small dependence on light intensities. The intensity

was altered by using different slits.

The quantum yields were not exactly independent of the intensity

for nonequal molar solutions with 0.47 m/l of FN and 0.71 m/l of DVE

in acetonitrile at 300 nm. The intensities were altered either by

the different slits or with a copper screen in front of the sample tube

in this case. Also, the quantum yields were changed with different

intensities at 236 nm, with 0.6 m/l of DVE and 0.6 m/l of FN. The data

of the light intensity dependence on qauntum yeild and rate are listed

in Table XII.

The linear dependence of intensity on quantum yield are shown in

Table XIII. The linear correlation coefficients were close to one

indicating that the equations can be used for comparing the quantum

yields at the same intensity for different wavelengths. The results are

shown in Table XIV. Apparently the quantum yield at 236 nm is larger

than at 300 nm.

Ferree and Butler observed that the quantum yield was constant or

declined slightly as the wavelengths decreased, until part of the divinyl

ether band is excited at 236 nm, at which point the quantum yield in-

58
creased drastically. This fact suggests that only excitation in either



























CO r-H LO C0 D m D CO
Cm =f r-C H D CO t- @l in N ln m El- Cc m H
o n C c- oc ri o N H C o Co o o

C) 0 CD H-, C CD C) C) C) C) C) C) C) C) CI








rI-









4o O O 4 CO -o cO c O LO O on o4 O
0 C) C) C) 0 0 0 C0 0 CD CD 0) 0 -0 0H

C) C) C) C) C) C C) C) C) C) 0D C) C) C) C)


4










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in co 4-

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+1 +1 +I +1 +1 +1
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I H r-i H H H- H H
C-lD C) C C) CD C) C) C)D


0 0 0 0 0 0 0 0 0



SH H
roo CM CO Ln .d- ilL


0 CO 4--


+1 +1 +1
0 0 0
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CO .CO CO


















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H *H


0 0
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r-
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1 0




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SO )
0-







c0






0 O*>
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ro
M, r0
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C 0-!
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co 0 C)n C

cm; O O


-- I H-
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O r-4 CO O
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I + b
bj D O M O
In 0 rH 0
r r-1 r I H
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--I n -i co c-
x C; x
o o o



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IH 4 r- H

0 I + r- I C- I

I II 0 II 0 II


11 CN I1 C II C1
o o o
0 0 0

0( CO C\N


- r- r-H r
0t f0 0

S00 0 00 0

H-1 H-I H H-- i H r-H


0
Co)


U
0

()

0

0
44
C



'H



r-i



C








M





0T









the charge transfer complex absorption band or the divinyl ether

absorption band leads to initiation of copolymerization.



Table XIV

Comparison of Quantum Yield and Rate at 236 nm and 300 nm

Compound Concentration Wavelength Intensity Quantum Rate
(nm) Photons/sec Yield mg/min.
14
FN 0.47 m/l 236 8.86 x 1014 0.118 0.479

DVE 0.71 m/1 300 8.86 x 1014 0.076a 0.304a

aCalculated from equations in Table XIII.





It has been suggested that an exciplex was responsible for the

copolymerization while no ground state charge transfer complex was

observed,76 such as the photocopolymerization of vinylcarbazol and

acrylonitrile. Since at 236 nm the only effective photoabsorbing

species was DVE, the initiation process must proceed via the excited

state of DVE. Although there was no evidence of exciplex of DVE and FN,

no significant homopolymerization was obtained with DVE alone, this

fact indicating that the excited DVE initiated copolymerization possibly

through the interaction with the ground state of FN.



236 nm
DVE -236 > (DVE)*


(DVE)* + FN (DVE* -> FN)

exciplex









At 300 nm the photoabsorbing species was complex, therefore the

initiation process proceeded via the excited state of the complex.



DVE + FN ---< (DVE FN) ---- (DVE-FN)*
<---- 300 nm



At both wavelengths, the excited species dissociated into initia-

ting radicals. Although the initiating radicals have not been identified

they could be a paired cationic radical and anionic radical.


kd
(DVE+FM)* -- 2R*


(1 d
(DVE*-*FN)


The ionic radicals initiated the copolymerization through free radical

processes because both air and a small amount of diphenylpicryl-

hydrazyl free radical (DPPH) retarded the reaction.


R O
R* + (DVE -- FN) --

CN



N CN


A small amount of FN (1%) did not initiate

excess DVE (99%) to a significant extent.

ether radical formation can be excluded at

the copolymerization.

R* + =-0-= -- R-


the homopolymerization of large

This indicated that the divinyl

least in the early stages of


_0"









The initiation through free fumaronitrile cannot be excluded but probably

is not able to compete with the low energy pathway of the complex

initiation process.

At 300 nm the light was totally absorbed by the complex for the

solution of 1.2 m/1 and of FN and 1.2 m/1 of DVE.


FN + DVE -- (DVE -- FN)


(DVE -- FN)* is the excited complex.



(DVE FN)* (DVE)
(FN)

(DVE-- FN)


300 nm d
30 nm (DVE -- FN)* 2R*
cc


Ground state molecules


Scheme II

I = The light intensity absorbed by the complex.

=I (light intensity absorbed by actinometer).

c = The quantum yield with only radiation deactivation considered.

The excited complex may be deactivated by collision processes.

As discussed before the exact structure of the excited state is not

known, but it may still be very polar and very likely to be deactivated

by the polar monomers and the ground state complex. The radiationless

deactivation process may be proposed as in Scheme II.

The rate of formation of the primary radicals (R*) can be derived by

applying the steady state assumption and assuming that the radiationless

rates of the deactivation of excited complex is proportional to the total

concentration of monomers, (T).









-d(DVE -- FN)* (T)DE
( dt )rl = kr(T)(DVE --, TN)*
dt rl rl



Therefore,



d(DVE -- FN)*
d(D I-c Fc (DVE -> FN)"(kd + k r(T)) 0
dt cc d rl



From Scheme II



R. = k (DVE -P FN) =. (kdI c )/(kd + K ,(T))
i d dcc d rl



At 236 nm the complex absorbed insignificantly but DVE absorbed part

of the light, Id = absd(DVE), and is responsible for the initiation

through the following equation.


k'
236 nm FN d
DVE I DVE* ---) (DVE* -> FN) 2R*
d d df

rl
radiationless deactivation

Dd is the quantum yield with only radiation deactivation considered.

In the same way as proposed at 300 nm, the rate of formation of the

primary radicals (R-) can be derived by assuming the rate of the
d(DVE* --> FN)
deactivation of exciplex, (- d( ----) is proportional
dt rl
to the total concentration of monomers (T).



d(DVE* > FN)
dtV- = k (DVE*)(FN)-(DVE*-- FN)(k' + k' (T)) = 0
dt df d rl



k'dIabs d d(DVE)
R. = k' (DVE* --: FN) = d abs d d
i d k' + k'rl (T)
d rl









Dependence of Feed Composition on Rates

It was of considerable interest to measure the rate of copolymeriza-

tion obtained for different feed compositions. As explained later, the

study of the rate as a function of the feed composition when the total

monomer concentration is kept constant should give information on the

role of the charge transfer complex in the mechanism of copolymeriza-

tion.

The effect of the variation of the concentration of the reactants

on the rate of a photochemical reaction is difficult to determine

unless the rates are corrected to a constant absorbed light intensity

from known variation of rate with the absorbed light intensity.

The rate of copolymerization was measured in acetonitrile. The

samples were prepared as indicated in the experimental section. The

solutions were irradiated at room temperature for a measured period

of time and the reaction was stopped by immediately opening and roto-

vapping to dryness. Methanol was added, and the insoluble polymer was

filtered and washed with methanol, and dried in an oven at 500C at least

for 4 hours. The actinometer solution was irradiated in the same tube

right after the reaction. The rate was obtained by measuring the

weight of the polymer after drying. The dependence of the light

intensity on rate is reported in Table XII. The linear relation is

shown in Table XIII.

Rates of products formed in secondary reactions (including the

polymerization) usually show some other than first order dependence

on intensity. In general, bimolecular termination by a reaction

involving active chain carrying species results in rates proportional

to the square-root of intensity. Termination which occurs from a first









order reaction leads to a rate which is dependent on the first power

of intensity. It was observed that the rates were dependent on an

order between 0.72 1 of intensity. It was close to first order for

the equal molar solution at 300 nm. Possibly both the bimolecular and

unimolecular termination are operating in photocopolymerization. The

first order termination is more possible because the propagating radical

may be terminated by chain transferring to solvent and the polar monomers.

The dependence of feed composition on corrected rate was listed in

Table XV and XVI and Fig. 15 and 16.
.16
The rates were compared at I = 1.52 x 10 photons/sec and
14
6.4 x 1014 photons/sec for irradiation at 300 nm and 236 nm respectively.

It was observed that at 300 nm, the maximum rate was at fd = 0.5

(equal molar solution), but at fd > 0.5 at 236 nm for both total

concentration [(T) = 2.40 m/l and 0.60 m/l]. The composition of copoly-

mers were in the same range (md = 0.35-0.48), and not much different

from each other for both wavelengths. Interestingly, at 236 nm, the

rate maximum fell on fd = 0.66 and 0.80 for higher total concentration,

(T) = 2.00 m/l, but on fd = 0.55-0.80 for lower total concentration,

(T) = 0.60 m/l. The ir and nmr spectra were almost identical. These

facts indicated that the same propagation process was employed. The

different positions of rate maxima were then due to the different

initiation porcesses.

Mechanisms

The kinetical derivation of the overall rate of copolymerization

can be done by assuming the simplest propagation as follows.





















\ CN k
\ k12
/ \ \CN
CN
CN M2
CN m2







CN



I + (DVE F N) k -2
CN


CN m


(Cq. 22)


0

+ (DVE-> FN) -


CN CN
CN
CN

M m*
1 1


(Eq. 23)














Table XV

The Rate of Copolymerization of DVE-FN System in Acetonitrile
at 300 nm, at I = 1.52 x 10 Photons/Sec.

Total Ratea Total Ratea
Concentration fd (mg/min) Concentration fd (mg/min)
(m/1) (m/l)

0.60 1.00 nil 1.20 0.80 0.179

0.60 0.90 0.051 1.20 0.60 0.313

0.60 0.82 0.117 1.20 0.50 0.376

0.60 0.80 0.098 1.20

0.60 0.70 0.131 2.40 0.98 0.087

0.60 0.67 0.154 2.40 0.70 0.475

0.60 0.60 0.150c 2.40 0.60 0.604

0.60 0.55 0.154 2.40 0.50 0.749

0.60 0.52 0.185 2.40 0.33 0.580

0.60 0.50 0.198 2.40

0.60 0.45 0.161 2.40

0.60 0.40 0.190 2.40

0.60 0.40b 0.053 2.40

0.60 0.30 0.167 2.40

0.60 0.20 0.147 2.40

0.60 0.00 --- 2.40
aThe rates were corrected to I = 1.52 x 106 photons/se with equation

log rate a /rate = log 1.52/I x 10.
b cal exp exp
Sample was open to air.
CAverage values.






83











(\] *
LnH






o E-'-
F
o
0 H II 0






o
Co

o po

OC






O *rl *H
LA CO+
Y / ", P 4r-



S\ 0 0
\ X 0
0




o--T--
; C

Sko



\ \ ,C-
S 0 4 -




o o 4-Co







(o
ac
0 0 I 000 0 4 -1


(~uI/rEC) uoT 4- ) ( q-











Table XVI

The Rate of Copolymerization of DVE-FN System in Acetonitrile
14
at 236 nm, at I = 6.4 x 10 Photons/Sec.

Total Ratea Total Ratea
Concentration fd (mg/min) Concentration fd (mg/min)
(m/l) (m/1)

0.60 1.00 nil 2.00 0.90 0.0413

0.60 0.90 0.0217c 2.00 0.80 0.0692

0.60 0.80 0.0274c 2.00 0.80b 0.0267

0.60 0.70 0.0231c 2.00 0.66 0.0686

0.60 0.60 0.0229c 2.00 0.50 0.0644

0.60 0.55 0.0303 2.00 0.40 0.0448

0.60 0.50 0.0246c 2.00

0.60 0.48 0.0235 2.00

0.60 0.45 0.0170c 2.00

0.60 0.41 0.0197 2.00

0.60 0.40 0.0179 2.00

0.60 0.31 0.0209 2.00

0.60 0.00 --- 2.00

The rates were corrected to I- 6.4 x 101 photons/sec with the equation
log rate /rate = 0.72 log 6.4/I x 10
b cal exp exp
Sample was open to air.
CAverage value.























































































0 0 0 0 0 0 0

0 0 0 0 0 0 0

(uyTm/S) uoTqezTjGwa m odoo jo Ga'H


-zr

\O *


H


Eo



L(\




4-)O
C\l


cd






0



-H 0

-r 4-)
cHO


4D, 4-)

a0 0)
u 0
O o




00







- 0
oC







r-t _

aip
E >








E0
O0









4->r

(Dr









In this copolymerization, the cyclized DVE radical (XXXI)

attacked complex and monomers to produce polymers with 1:1 and 1:2

compositions, respectively. The 1:1 composition cannot be explained

by the polarity of the radical and complex, because the negatively

polarized radical (XXXI) would attack the positively polarized carbon

carbon double bond of an acceptor monomer since polymerization of DVE

under the same condition is negligible. The propagation of the copoly-

merization can be interpreted as a competition between the acceptor

monomer FN and the CTC toward the cyclized DVE radical (XXXI).

Although the cyclization of the DVE radical (XXXI) could react

preferably with the acceptor such as MAH because the reaction of a

radical and a monomer of opposite polarities would stabilize the

transition state,0 the FN may not be so preferable because of the

less polarization then MAH. Thus, the reactivities of FN and the complex

are compatible. As a result, a competition between FN and CTC control

the structure of the copolymer of DVE-FN system. On the other hand,

the complexation of the HOMO of DVE and LUMO of FN would increase the

energy of HOMO of DVE71 and make the CTC more reactive toward the

destabilized cyclized radical (XXXI) than the uncomplexed DVE.

In equations 22 and 23; the cyclization may proceed by both

concerted and stepwise processes. A fast cyclization has been observed

for this cyclocopolymerization, which indicated a concerted mechanism.

But some results showed the stepwise mechanism, especially for the

fact that both cis and trans disubstituted ring units were obtained in

the analysis of spectra. A stepwise cyclization cannot be ruled out.

However, by assuming a fast stepwise cyclization (probably just a little

slower than the cis-trans rotation around the disubstituted single bond)










of radical XXXII, the same result will be concluded as with the

concerted process as far as rate is concerned.







CN

CN

XXXII



By a;zuinir, only the cross-termination



t12
mi + m2 -- dead polymer



and the steady state:



kl2(ml')(M2) = k21(m2.)(M)


k (M )
Ri = R = 2k 2(ml.)(m ) = 2k 21(M (m.)2
21 1


Then, by assuming (DVE --- FN) = K (FN)(DVE)
c


R.k
i 21 1/2 1/2 1/2
Rate = ( )/2(DVE) /2(FN)K [2k2 + k lK (DVE)]
2k k c 12 11 c
12 t12

By definition (FN) = (1 fd)(T), (DVE) = fd(T)

where (T) = total concentration= (FN)+(DVE), f = (DVE)/(T)
The rate maximum is a function of (T) and will be at fd = 0.5 by keeping
The rate maximum is a function of (T) and will be at f = 0.5 by keeping




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FILES



STUDY OF CYCLOCOPOLYMERIZATION
by
YUAN CHIEH CHU
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE
REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1977

Dedicated to
the mother of Lawrence Chu

ACKNOWLEDGEMENTS
The author would like to express his special gratefulness to
Professor George B. Butler for his encouragement and invaluable
guidance during the execution of this work.
The author also would like to express his appreciation to his
advisory committee and other faculty members in the Department of
Chemistry whose assistance and suggestions contributed much to this work.
He wishes to thank Mrs. Carol Albert for typing this thesis, Professor
G.B. Butler for checking the English composition, Dr. S.F. Tien for
his suggestions on the theoretical aspects, and T. Baugh for his work
13„
on C nmr spectroscopy.
Finally, the author wishes to express great appreciation to his
wife, Rolan, whose forbearance and understanding made this work
possible.
The financial support for this work from the Department of
Chemistry and Professor G.B. -Butler's National Institutes of Health
grant is gratefully acknowledged.
in

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vi
LIST OF FIGURES viii
ABSTRACT x
CHAPTER
I. INTRODUCTION 1
History of Cyclopolymerization and
Cyclocopolymerization 1
Mechanism of Cyclopolymerization 11
Mechanism of Cyclocopolymerization 16
Statement of Problem 22
II. THE STRUCTURE OF COPOLYMER OF DIVINYL ETHER-
MALEIC ANHYDRIDE SYSTEM 24
Introduction 24
Results and Discussion 25
The Mechanism of Cyclization 47
III. THE COPOLYMERIZATION OF DIVINYL ETHER-
FUMARONITRILE . 52
Introduction 52
Results and Discussion 53
IV. EXPERIMENTAL 100
Materials 100
Equipment and Data 101
Synthesis Related to Monomer Preparation .... 103
Copolymerization 110
IV

Page
APPENDIX - STEREOCHEMISTRY BACKGROUND FOR 5,5- AND
5,6-BICYCLIC SYSTEM IN THE COPOLYMER OF DVE-MAH 119
BIBLIOGRAPHY ' . . 123
BIOGRAPHICAL SKETCH 127
V

LIST OF TABLES
Page
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
IX.
X.
XI.
XII.
XIII.
The Relation Between Concentration and Cyclization. . 12
The Energetical Parameters for Cyclopolymerization. . 15
The Reactivity Ratio of Copolymerization 18
The Comparison Between J and JIITI 28
HU HH
The Chemical Shifts for the Methine Protons of
DVE-MAH Copolymer 33
Chemical Shift Differences Between cis and trans
Disubstituted Vicinyl Carbons in P-^C nmr Spectra. . . 44
Determination of Equilibrium Constant of FN-DVE in
Acetonitrile with Constant FN Concentration
(0.00101 m/1) 57
Comparison of Copolymer Initiated by Different Methods
in Acetonitrile 61
The Compositions of Copolymers Prepared in Aceto¬
nitrile at Room Temperature within 10% Conversion . . 64
The Limiting Yield of Copolymerization with Excess
DVE in Feed Composition 67
13
Comparison of C nmr Spectra between Homopolymer of
DVE and the Copolymer of-DVE and FN 70
The Light Intensity Dependence on Quantum Yield and
Rate in Acetonitrile at Room Temperature 73
The Linear Relations of Intensity (I) to the Quantum
Yields ($) and Rates 74
XIV. Comparison of Quantum Yield and Rate at 236 nm and
300 nm 75
XV. The Rate of Copolymerization of DVE-FN System in
Acetonitrile at 300 nm, at I = 1.52 x lO^
Photons/Sec
82

Page
XVI. The Rate of Copolymerization of DVE-FN System in
Acetonitrile at 236 nm, at I - 6,4 x 10l^
Photons/Sec 84
XVII. The Dependence of Total Concentration on Rate. ... 90
XVIII. The Determination of Reactivity Ratio r^ 97
XIX. The Copolymerization of DVE-FN System with Additives 111
XX. The Copolymerization of DVE-MAH System at Different
Temperature 116
va 1

LIST OF FIGURES
Figure
Page
1
IR spectrum of the copolymer of DVE-MAH prepared
xylene at 130°C
in
29
2
60 MHz nuclear magnetic resonance spectra of (a)
copolymer, (b) DDVE-MAH copolymer in acetone d^ .
DVE-MAH
32
3
100 MHz nuclear magnetic resonance spectrum of DDVE-MAH
copolymer
35
4 300 MHz nuclear magnetic resonance spectra of (a) DVE-MAH
copolymer, (b) DVE-MAH DMAH copolymer in acetone-d^ . .
13
5 C nuclear magnetic resonance spectra of (a) DVE-MAH
copolymer, (b) poly(maleic anhydride), (c) hydrolized
DVE-MAH copolymer
13
6 C nuclear magnetic resonance spectrum of 2,3-dimethyl
succinic acid
13
7 C nuclear magnetic resonance spectra of DVE-MAH
copolymer prepared at (a) 130, (b) 100, (c) 72, (d) 25°C
8 The absorption of the complex of DVE-FN in acetonitrile
(a) 0.6 m/1 of DVE, (b) 0.6 m/1 of FN, (c) (DVE) =
(FN) = 0.6 m/1 54
9 The determination of the stoichiometry of the DVE-FN
complex in acetonitrile by continuous variation method
at 300 nm (DVE) + (FN) = 0.60 ± 0.03 m/1 55
10 Charge transfer absorption of DVE-FN complex in aceto¬
nitrile 58
11 IR spectra of the DVE-FN copolymer initiated (a) at
300 nm, (b) at 236 nm, (c) by AIBN 63
12 60 MHz nuclear magnetic resonance spectra of the DVE-FN
copolymer initiated (a) at 300 nm, (b) at 236 nm,
(c) by AIBN 63
13The compositions of the DVE-FN copolymer initiated at
(a) 236 nm, (b) 300 nm
36
40
42
46
viii
65

Figure
Page
14 C nuclear magnetic resonance spectra of the copolymer
initiated (a) at 236 nm, (b) by AIBN, (c) at 300 nm. ... 69
15 The dependence^gf feed composition on rate at 300 nm
(I - 1.52 x 10 photons/sec) for total concentration
(a) 2.40 m/1, (b) 1.20 m/1, (c) 0.60 m/1 83
16 The depencenc^of feed composition on rate at 236 nm
(I = 6.4 x 10 photons/sec) for total concentration
(a) 2.0 m/1, (b) 0.6 m/1 85
17 The dependence of total concentration on rate (x) at 300 nm,
f¿ = 0.5, (A) at 300 nm, f¿ = 0.6, (o) at 236 nm,
f^ = 0.5, (•) at 236 nm, f¿ = 0.8 91
18 The determination of reactivity ratios (T) = 2.0 m/1,
at 300 nm (T) = 2.0 m/1, at 236 nm, (T) =
1.1-4.5 m/1, with AIBN 98
19 60 MHz nuclear magnetic resonance spectra of (a) DVE,
(b) DOVE with 250 ppm sweep width, (c) DDVE with 100 ppm
sweep width 105
20 60 MHz nucelar magnetic resonance spectra of (a) 2,2,2',2'-
tetradetueriodiethylene glycol, (b) diethylene glycol. . . 107
21 60 MHz nuclear magnetic resonance spectra of (a) bis-
(2-bromo-2,2-dideuterioethyl)ether, (b) bis(2-bromoethyl)-
ether 109
22 The viscosities of the DVE-MAH copolymer in DMSO prepared
in (a) benzene at 76-78°C with 77% conversion, (b) in
benzene at 51-54°C with 25% conversion, (c) in benzene
at 61-64°C with 47% conversion, (d) in CHC1 at 60-61°C
with 43% conversion, (e) in benzene at 28-29°C with 31%
conversion initiated by light 118
IX

Abstract of a Dissertation Presented to the
Graduate Council of the University of Florida in Partial Fulfillment
of the Requirements for the Degree of Doctor of Philosophy
STUDY OF CYCLOCOPOLYMERIZATION
By
Yuan Chieb Chu
June, 1977
Chairman: George B. Butler
Major Department: Chemistry
The well-known alternating 1:2 cyclocopolymer of divinyl ether
(DVE) and maleic anhydride (MAH) has been found to possess interest¬
ing anti-tumor and biological activities. Recent research on the
structure of the cyclopolymer has raised a question about the ring
size of this cyclocopolymer. In this research program the structure
of this copolymer was reexamined by use of spectroscopic methods.
A linear, soluble copolymer was obtained by the copolymerization in
solvents with active hydrogens, such'as chloroform and xylene. The
ir spectra showed the existence of both monomers in the copolymer
based on the strong bands at 1775, 1855, 1230 cm ^ (cyclic anhydride),
and 1090 cm ^ (cyclic ether).
By use of deuterated copolymers, the H-nmr peaks at 5 2.31, 3.47,
4.06, and 4.49 ppm with an area ratio of 2:1:1:1 were assigned for
the hydrogens of methylenes, methines on the backbone anhydride unit,
methines on the ring anhydride unit, and methines adjacent to oxygen
on the cyclic ether ring, respectively. Through the examination of
x

the possible isomeric structures of the bicyclic ring, the splitting
of each peak group was further assigned for cis and trans di-substi-
tutions on the anhydride unit.
The splitting pattern on the 300 MHz nmr spectrum of divinyl
ether - 2,3-dideuteriomaleic anhydride copolymer confirmed the unsym-
13
metrical six-membered ring structure. C nmr spectra was discussed
and was consistent with the conclusion from the H-nmr spectra.
A chair-form six-membered ring with trans isomer next to each
side of the ring oxygen with a small portion of cis isomer was assigned
for the structure of DVE-MAH copolymer.
13
Based on little or no change of the C nmr spectra of the
copolymers prepared at different temperatures, it was concluded that
there was no significant change of structure caused by temperature
effect. This led to the sole assignment of the six-membered ring
structure of the copolymer as an energetically favored product.
A mechanism for the cyclization was proposed based on the H0M0-
LUMO interaction of the comonomers and the radical intramolecular
addition on the preoriented double bond. This mechanism led to the
formation of six-membered ring structure of the copolymerization as
the sole product.
The participation of the charge transfer complex in the cyclo¬
copolymerization was investigated with the divinyl ether-fumaronitrile
system by light initiation. The evidence and the composition of the.
complex were obtained by the UV spectroscopic method. The structure
of the copolymer was proposed on the basis of elemental analysis and
13
C nmr spectrum, as a mixture of 1:1 cyclocopolymer and 1:2 cyclo¬
copolymer structures, both with six-membered rings. The initiation
xi

mechanism involving polar deactivation of excited molecules and the
propagating mechanism were proposed to explain the rate maximum
phenomena and the relation between copolymerization rate and total
concentration of the comonomers at 236 nm and 300 nm irradiation.
A consistent result was obtained by the proposal of the participation
of the CTC in both the initiation and propagation processes.
XI1

CHAPTER I
INTRODUCTION
History of Cyclopolymerization and Cyclocopolymerization
It is well known that multifunctional monomers such as unconjugated
divinyl monomers are crosslinking agents in vinyl polymerizations.**-
However, certain compounds, such as diallyl phthalate and ethylene
2
diacrylate, undergo cyclization during polymerization, with the result
that 40-75% of the divinyl compound used is incapable of crosslinking.
3
Butler and coworkers found that several diallyl quarternary ammonium
salts polymerized to yield soluble and hence linear polymers containing
little or no residual unsaturation. Under the same conditions monoallyl
ammonium salts failed to polymerize. To explain the unusual results,
4 .
Butler and Angelo proposed an alternating intramolecular mtermolecular
chain propagation mechanism to form a cyclic structure in the chain
(eq. 1). This type of process is now commonly termed cyclopolymerization.
Since these initial investigations, a large number of 1-6 non-
conjugated dienes of type I have been cyclopolymerized using appropriate
catalysis to yield soluble, mostly saturated polymers with cyclic struc¬
tures in the main chain.
In cyclocopolymerization, the comonomer contributes to formation of
5
the cyclic structure along with the nonconjugated diene. Butler reported
the first example of cyclocopolymerization. By copolymerizing divinyl
ether (DVE) and maleic anhydride (MAH), using a free radical initiator,
a soluble polymer was obtained. A mechanism similar to the cyclopolymer¬
ization was proposed which is shown in equation 2.
1

2
This cyclocopolymer has been found to possess interesting
. . 5
biological activity.

3
Intermolecular
propagation

4
0
The proposed mechanism was based on the following facts:
(a) a soluble copolymer was formed, (b) little or no residual unsaturation
was detected in the copolymer and characteristic absorption bands for
cyclic anhydride and ether were observed in infrared spectra, (c) the
composition of the copolymer was close to.a diene-olefin molar ratio
of 1:2 over a wide range of comonomer feed composition, Cd) quantitative
conversion to copolymer was obtained, (e) the cleavage by hydriodic acid
and the incorporation of iodine into the copolymer indicated the pres¬
ence of cyclic ether groups, and (f) neither monomer homopolymerizes
readily under the same condition as copolymerization.
Following Butler's discovery, the copolymerization reactions for
a wide variety of 1,4-dienes and olefins have been reported. Butler
and coworkers further studied some mono-olefin-1,4-diene systems to
produce 1:2 (1,4-diene:monoolefin) copolymer with generalized structure II.
tors, a soluble copolymer of a nonconjugated diene, 1,5-hexadiene, and
sulfur dioxide. Elemental analysis of the copolymer samples substantiated
the existence of a material containing exactly two sulfur dioxide portions
to one of diolefin. The six-membered ring structure was confirmed by
comparing the ir spectra of the copolymer sample with pentamethylene
sulfone.

5
Price and coworker prepared the copolymers of N,N-divinyl
aniline with diethyl fumarate in bulk and solution with azobis-isobutyro-
nitrile (AIBN) at 60°C. Diethyl fumarate, having widely different
polarity from that of divinyl aniline, and being reluctant to homo-
polymerize, polymerized with divinyl aniline in widely different monomer
concentration ratios to give copolymers of nearly constant 2:1 molar
ratio composition. The colubility of this copolymer and the negative
results of analysis for residual double bond by infrared absorption in
the 6.0-6.2 y region, supported the cyclic copolymer structure IV.
IV
The copolymerization of divinylphenylphosphine with acrylonitrile
9
was studied by Butler, et al. The copolymer produced was soluble m
DMF and showed no residual unsaturation. Elemental analysis indicated
the copolymer contained 0.265 mole fraction of divinylphenylphosphine
and 0.732 mole fraction of acrylonitrile. The structure of this
copolymer and the reaction for its formation are as follows (eq. 3):

6
Y5
J \
+
CN
/
nCH =CH
R-
>
Rigid or multicyclic systems have been reported. Meyersen and
Wang10 prepared several copolymers of fused ring systems such as bicyclo-
pentene with sulfur dioxide or maleic anhydride in solution by free
radical initiation. Copolymer was obtained in the ratio of 1:2 as in
structure V in equation 4.
X = S02 or
ft
Yamaguchi and Ono11 reported the copolymerization of sulfur dioxide
and dicyclopentadiene (DCPD) in liquid sulfur dioxide with AIBN or other
radical initiators at o° or 20°C. Soluble copolymer was obtained with a
composition ratio of DCPD to sulfur dioxide of 1:2, and containing

7
virtually no residual double bond. The structure of this polysulphone
was proposed as VI.
-SCL
12 . .
Butler and Pledger proposed .1:1 alternating copolymer of maleic anhydride
with 5-ethylidene-, 5-methylene-, and 5-vinyl-bicyclo(2,2,1)-2-heptene.
Evidence supported a tricyclic structure which incorporated maleic
anhydride as part of a six-membered ring repeating unit, for example
structure VII.
The essential structure of the cyclocopolymers were proposed based
on the following methods.
1. Elementary analysis - Most of the copolymers which have been studied
have a 1:1 or 1:2 comonomer composition in the copolymer regardless of
the wide range of feed composition, solvent, or initiator concentration
2. Little or no residual absorption in carbon carbon double bond -
This indicates that all the double bonds in the diene were incorporated

8
into the copolymer. Only high degree of cyclization and crosslinking
can explain this observation. The residual unsaturation can be
detected by the absence of, or little ir absorption in the 6.0 to 6.2 y
region and nmr. Negative results of catalytic hydrogenation has been
used to show the absence of residual carbon carbon double bond in the
copolymer.
3. The solubility of copolymer and the absence of gelation at high
conversion rule out the crosslinked structure.
4. Existence of both monomers in the resulting polymer - This can be
shown by the characteristic absorption bands of the comonomers in the
infrared spectra. For example, the 1100-1085 cm \ strong, broad band
for cyclic ether and the 1860, 1795 cm ^ bands for cyclic anhydride in
the ir spectra of DVE-MAH copolymers indicating the existence of both
comonomers in the copolymer.
5. The alternating ratios are always supported by elementary analysis.
Chemical method may support the proposed structure. Butler and
13
Guilbault hydrolyzed and dehydrohalogenated the copolymer of DVE-
chloromaleic anhydride, followed by the treatment with KMnO^ to get the
vic-diol copolymer. The degradation result of this vic-diol copolymer
upon periodic acid cleavage supported the 1:1 structure with only DVE
units on the backbone.
C00H
C=0 C=0
¿00H “°H-
1. KMnO,
4
2.
Eq. 5

9
Both five- and six-membered rings can be formed during the cycliza-
tion step. Unfortunately not much work has been done along this line
to distinguish between these possibilities.
7
Stille and Thomson used the ir absorption spectra of model compounds,
VIII and IX, to compare with the 1,5-hexadiene-suIfur dioxide copolymer.
They concluded that the six-membered ring structure (III) was present in
the copolymer.
VIII IX
This method has also been used by Meyersen and Wang'*'0 in their
fused ring system-sulfur dioxide copolymer as mentioned in the last
section.
14
Butler and Fujimori studied3 ring size by the readiness of the dehy-
drohalogenation of the cyclocopolymer. The quantitative elimination
of only half the chlorine content of dichloro-maleic anhydride-DVE
cyclocopolymer provided the first support for the proposed six-membered
cyclic repeating unit. There would have been no such elimination if the
repeating unit were five-membered. If both the halogens and the
hydrogens at the 2-position to the oxygen were eliminated, the product
would be a furan derivative which should be detectable due to its
aromatic character.

10
aq. NaOH
>
-HC1
Eq. 6
Eq. 7
On the other hand, the ring structure of the cyclopolymer has been
intensively investigated by chemical and spectroscopic methods. Butler,
15
Crawshav^ and Miller conclusively proved the existence of cyclic struc¬
ture of cyclopolymer prepared by free radical initiation for diallyl
quaternary ammonium salts. A nondegraded polymer was obtained by
treatment with KMnO^. However, the ring size was not determined by
13 16
these authors. Later, by C nmr spectroscopy, both the five- and
six-membered rings were found in- these cyclopolymers by comparing with
model compounds. Dehydrogenation of the cyclopolymer followed by the
identification of the resulting aromatic rings enabled Marvel and Vest
to confirm the six-membered ring structure in the cyclopolymer of
2,6-dicarbomethoxy-l,6-heptadiene prepared by free radical initiation.
17
Me OMe
,0° c°
COOMe
J200
Me
KC10,
CO
Eq. 8

11
Spectroscopic methods have been applied to studying the ring
18
size for the cyclopolymer. Butler and Myers used both ir and nmr
spectroscopy to analyze the cyclopolymer obtained from dimethacrylamide
and its N-methyl and N-phenyl derivatives. They found that the polymers
were composed of both five- and six-membered rings. Electron spin
. 19, 20
resonance studies
have shown that the radicals from N-substituted
N,N-diallylamine in the presence of TiCl^/H^O^ or TiCl^/N^NOH initiation
are five-membered ring cyclic species. It is possible that the radicals
involved in polymer formation have very short lifetimes (thereby not
detectable by ESR) and those radicals which are detectable are stable
but non-propagating species.
The extended chemical shift range, the absence of the simplicity
13
of proton decoupled C nmr spectra, in which each carbon resonates as a
13
singlet, makes the C nmr spectroscopy extensively useful for study of
21 13
polymer structures. Johns, Willing, Middleton,and Ong used the C
natural abundance pulsed Fourier transform nmr spectroscopy to distin¬
guish the different structure features of the polymers formed by radical
induced cyclopolymerization of a series of N,N-diallyl amines by
comparing with the model compounds. The polymers of N,N-diallylamines
all contained cis and trans -substituted pyrrolidine rings with the ratio
5:1. The polymers of N,N-bis(2-allyl)amine gave complex spectra due to
the presence of both cis and trans pyrrolidine and piperidiene rings.
Mechanisms of Cyclopolymerization
Since the discovery of cyclization in the cyclopolymerization, many
studies have been made on the nature of the cyclization step by theoreti¬
cal consideration and experimental methods.

12
A statistical approach to cyclopolymerization was taken by Butler
22
and Raymond. They concluded that to explain the high degree of cycliza-
tion at high monomer concentration (Table I), a more favorable pathway
from 1,6-diene to cyclic polymer might exist than would be predicted
on a purely statistical basis.
Table I
The Relation Between Cyclization
and Concentration
Assumed
Monomer
Cone. m/1
Cyclization %
Cone. m/.l
Cyclization
Diallyl quaternary
ammonium salts
>5.0
96-100
pure
monomer
<50
Diallyl silanes
1.2-2.3
>95
1.00
70
Acrylic anhydride
n,8.0
98-100
0.10
96
Diallyl phosphine
bulk
100
0.001
100
Gibbs and Barton explained this by considering the presence of the
large pendant group which would tend to prevent intermolecular reaction
and will frequently be presented to the reactive species in a conforma¬
tion which is favorable for polymerization (cyclization). Butler
24 ...
et al. studied the effect of the stability of the cyclized radical on
the rate of cyclopolymerization. The overall rates of divinyl monomers
were considerably greater than that of the corresponding monovinyl
monomers, the ratios varying from 2 to 10. They estimated the effective
concentration of the intramolecular double bond with respect to the
radical propagation, and values greater than 20 M at 50°C were obtained.
This incredible effective concentration indicated that a considerable
preorientation prior to reaction exists. This favorable preorientation
may be related to an electronic interaction between the developing

13
radical site and the intramolecular double bond or in the ground state
25
before the initiation as proposed by Butler.
In an effort to explain the strong polymerization of 1,6-heptadienes
25
relative to their monoolefinic counterparts, Butler proposed that
an electronic interaction between the unconjugated double bonds of
1,6-dienes or between the intramolecular double bonds and the reactive
species after initiation might exist.
These interactions would reduce the entropy change in going from the
ground state to the activiated state required for the intramolecular
propagation. The ground and activated state energies both would be
26
reduced. Mikulasova and Hvirik calculated the total activation energy
for radical polymerization of diallyldimethylsilane and found it to
be ca. 9 Kcal/(mole double bond) less than that for allyltrimethylsilane.
27
The electronic interaction is supported by UV absorption evidence,
2 8
but it is not necessary for cyclopolymerization as shown by Gibbs.
They found that in the case of methacrylic anhydride versus methacrylic
acid, there was essentially no difference in total activation energies
29
in the polymerizations. Marvel and Stille obtained a cyclic polymer
from 2,5-dimethyl-l,5-hexadiene, and suggested an unusual driving
force from diene monomer to cyclic polymer.
The activation energy for cyclization is not necessarily smaller
than the intermolecular addition for same radical as shown by several
30
authors based on the kinetic scheme developed by Mercier and Smets.

14
They derived the kinetic relationships between intramolecular and
intermolecular propagation for the free radical polymerization of
acrylic anhydride.
Eq. 9
The rate ratio of the intermolecular propagation (R^) to the intra¬
molecular propagation (R^) was derived;
R./R
i c
2 [monomer] —
. -E./RT
A. e i
B E /RT
A e c
c
where the difference in activation energies (E -E^) can be calculated.
Several E -E. values are listed in Table II. These results indicated
c 1
that the intramolecular propagation step requires greater energies

15
than the intermolecular step (Ec>E^). However, the rate of cyclization
is considerably larger than for intermolecular propagation (]< /1c^> 1) .
The values for the ratio Ac/A^ indicated a high entropy factor favoring
cyclization. The decrease in entropy for a cyclization step would
perhaps be expected to be smaller than that for addition of a new
monomer unit. Only rotational motion will be lost in cyclization; on
adding a new monomer molecule to the chain, the loss of translational
and rotational degrees of freedom will result. Therefore, as far as
entropy is important, cyclization would be favored over intermolecular
propagation.
Table II
The Energetic Parameters for Cyclopolymerization
Monomers
E ~E, Kcal/mole
C 1
A /A. mole/1
C 1
k /k. mole/1
C 1
Acrylic anhydride
2.4
167
5.9
o-Divinyl benzene
1.9
50
2.8
Diallyl phthalate
0.3
Methacrylic anhydride
2.6
256
2.4
Guaita has studied the temperature independent factor of
cyclization parameters for the free radical copolymerization of acrylic
anhydride and divinyl ether. The results indicated that the high frac¬
tions of cyclization in cyclopolymers from symmetrical unconjugated
dienes can be thermodynamically accounted for by an entropic effect
largely exceeding the energetical one. The entropy decrease was smaller
in the intramolecular reaction than in the intermolecular reactions.
25
These entropic effects are consistent with Butler's postulation of
the preorientation of two double bond by electronic interaction in both

16
ground and activated states. The nature of this preorientation between
the double bonds has been though to be due to a charge transfer complexa-
tion in the copolymerization, especially in the cyclocopolymerization to
produce alternating copolymers.
Mechanism of Cyclocopolymerization
32
Barton and Butler described a general copolymerization composition
equation of 1,4-dienes and monoolefins where the cyclic repeating unit
is bimolecular in construction. The kinetic scheme considered is shown
in equation 10.
11
ml + M1 * mi
12
m! + M2 » m3
. 32
m3 + M2 *
kcl
m + M, ——>
cl
m
m
2
1
m"
c
m.
c2
mc + M2 m2
21
m2 + M1 > mi
"2 + ”2 m2
(Eq. 10)
is the diene CH0=CH-X-CH = CH9 where X is CH9, 0, S09, etc. M9 is
the monoolefin, CHY^CHZ. The m^ is the radical j'-'CH^CHXCH^CH^, m9 is the
radical ~~-~-CHYCHZ, m^ is the uncyclized radical
Z
and m^ is the cyclized radical
A five-membered ring structure for rrr is possible.

17
The derived equation which related copolymer composition to monomer
feed composition in terms of five reactivity ratio parameters was given
as equation 11.
(1 + r x) [ ¿ + - (1 + - )]
1 M9 a r2
n = — ~ (Eq- ID
- C - + — + 2] + ¿ [1 + ( 1 + — )(1 + r x)-1]
a r3 x M2 x c
where x = M /M9 is the mole fractional ratio of monomers in the feed,
n = /1^2 is the mole fractional ratio of monomers in the copolymer at
low conversion, = k^/k^, r2 = k^/k^, r3 = k32/k31> rQ = k^/k^,
and a = kc/k . The equation may be approximated to simpler forms in
the following cases.
a.If kc>:>k39 so that a is very large and cyclization is the predominant
reaction of the radical, m^, the equation (11) gives
n = (1 + r x)(1 + r x)/[r x + (r /x) + 2] (Eq. 12)
1 c c 2
This is equivalent to considering the addition of monoolefin to diene
radicals to be a concerted bimolecular step proceeding through a cyclic
transition state and producing the cyclic repeating units.
b. If in addition there is a strong alternating tendency so that
r^-r^-r^-0 then equation (11) reduces in the limit to n= 1/2. This
predicts an alternating copolymer composition of 2:1 molar in contrast
to 1:1 for the similar limiting case of the classical binary copolymer
composition equation and that for the cyclopolymer composition equation.
c. If the diene has a negligible tendency to add to its own radicals and
ri~rc~^ an<^ there as also predominant cyclization, then equation (12)
gives
n = l/[r0/x) + 2]
(Eq. 13)

18
All three cases have been found as in Table III.
32
Table III
The Reactivity Ratio of Copolymerization
Case a Case b Case c
System
rl
r2
r3
System
System
r2
DVE-AN
0.024
0.938
0.017
1,4-PD-MAH
1,4-PD-AN
1.13
DVS-AN
0.364
0.067
0.067
DVE-MAH
DM-1,4-PD-AN
3.31
DVE-PMI
DVE-4-VP
32.0
DVE = Divinyl ether-, AN = Acrylonitrile; 1,4-PD = Dimethyl-1,4-penta-
diene; MAH = Maleic anhydride; PMI = N-Phenyl maleic imide;
4-VP = 4-Vinyl pyridine: DVS = Divinyl sulfone; DM-1,4-PD =
Dimethyl-1,4-pentadiene.
In cases (b) and (c) very low values for r^ have been reported.
This low value is remarkable in the case of monomers such as acryl-
nitrile, and indicates that almost all the AN radicals in m^ react
to form a ring. The actual ring formation may be either a.stepwise
reaction or a concerted reaction to form the product. Orientation
of monomers via a charge transfer complex (CTC) prior to free radical
reaction explains this unusual cyclic structure and also accommodates
the kinetic data (eq. 14).

19
Evidence for the participation of a CTC in the copolymerization
35
between styrene and MAH was presented by Tsuchida and Tomono. They
concluded that the CTC and uncomplexed MAH took part in the copolymer-
zation. Evidence for participation of a CTC in the cyclocopolymeriza-
3 6
tion of 1,4-dienes with monoolefin was presented by Butler and Joyce
on the comonomer pairs, DVE-MAH, DVE-MI, DVE-FN and dihydropyran
(DHP)-MAH. Butler and his group have intensively studied the partici¬
pation of CTC in cyclocopolymerization. The evidence of the existence
of the CTC was confirmed by both UV and nmr spectroscopies. The
equilibrium constant of the complexation can be obtained by these
spectroscopic methods. The complex is formed by interaction of an
electron-rich donor (D) and an electron -deficient acceptor (A).
D + A ——* [D*+ , A*"]
^
The composition of all the complexes formed by 1,4-diene and monoolefins
were 1:1 complexes. The alternating copolymer compositions found were
2:1 in olefin to 1,4-diene ratio for most of the 1,4-dienes with MAH or
FN. This is consistent with the postulation that the CTC undergoes a
1:1 alternating copolymerization with the electron acceptors such as
MAH and FN, which can thus account for the structure of the copolymer.
Some 1:1 copolymer has been obtained which can be considered as the
product of the homopolymerization of the 1:1 complex.
One necessary requirement for these alternating copolymerizations
is that neither of the comonomers should be homopolymerizable to a
significant extent under the same condition of the copolymerization. If
the acceptor is homopolymerizable such as AN, MMA and 4-VP, acceptor will

20
be incorporated in the copolymer to a greater extent than the expected
value for 2:1 copolymer, i.e. 67%.
The contribution of complex can be further demonstrated by
terpolymerizations. The terpolymerization of styrene, MAH, and
35
2-chloroethyl vinyl ether (ChEVE) studied by Tsuchida and Tomono
can be explained by treating the system as a copolymerization of two
complexes, styrene-MAH and ChEVE-MAH. Butler and Campus studied the
terpolymerization of DVE-MAH-AN system. The DVE-MAH ratio in the
terpolymer was always less than 1:1 and had a lower limit of 1:2
regardless of the feed ratio of the termonomers. These results were
interpreted in terms of the participation of the CTC of DVE-MAH in the
copolymerization process with either MAH or AN.
The MAH reacted with DVE in the absence of normal radical initia-
38
tion to form cyclic 2:1 copolymer. It was postulated that initiation
via a molecular complex occurred (eq. 15).
• Active forms
(Eq. 15)
The initiation of CTC can be demonstrated by photo-initiation of this
39 '
system and the DVE-FN system. Zeegers and Butler photo-initiated the
DVE-FN system with different wavelengths. They showed that both the
complex formed between DVE and FN and the noncomplexed species were
able to initiate the polymerization by light initiation.
40
Miller and Gilbert observed that vmylidine cyanide spontaneously
copolymerized with vinyl ethers when the two comonomers were mixed at

21
room temperature. Yang and Gaoni observed that 2,4,6-trinitrostyrene
as the acceptor monomer spontaneously copolymerized with 4-VP as the
42
donor monomer. Butler and Sharp reported the spontaneous copolymeriza¬
tion of DVE and DVS.
The concerted cyclization has been argued by Butler and
Guilbault. ^ They found that chloromaleic anhydride copolymerized
with DVE to form soluble copolymers of 1:1 composition with no residual
unsaturation. The ease with which the copolymer underwent dehydro-
halogenation indicated that the'hydrogen and chlorine atoms on the
anhydride unit are in a trans configuration as a result of a stepwise
cyclization process.
The steric effect of highly substituted acceptors, tetrahydro-
naphthoquinone (THNQ) and dimethyltetrahydronaphthoquinone (DMTHNQ) on
43
the copolymerization with DVE was studied by Fujimori and Butler.
They found that the copolymers was in constant 1:1 composition regard¬
less of the feed composition. A terpolymerization of these two acceptors
with DVE was studied. Both the copolymerization and terpolymerization
and the composition can be explained by assuming that competition
between an acceptor monomer and the CTC towards the cyclized DVE radical
in the propagation step appears to favor the CTC in CTC mechanism.
14
These authors studied the steric effect of substituted MAH on the
copolymerization with DVE. They found that (i) a strong complex gave
1:1 cyclocopolymer having a copolymer backbone consisting of only DVE
units, (ii) a sterically hindered acceptor would produce 1:1 cyclocopolymer,
and (iii) a weak CTC and reactive acceptor would produce 1:2 cyclocopolymer.
They did not mention the reactivity change of the acceptor due to the
substitution. The alternating tendency and the rate increased by using

22
a large amount of ZnCl^ with the DVE-FN system. A 1:2 alternating
copolymer was obtained spontaneously. This system studied by Butler
44 . ...
and Fujimori was consistent with the participation of a CTC m the
copolymerization mechanism.
3 8
Solvent effects have been studied by Butler's group. The K
value (equilibrium constant of CTC formation) decreased with increase
of the dielectric constant of the solvent for MAH-DVE system. The
rate of the copolymerization and number average molecular weights
decreased in more polar solvents. In all cases, 2:1 copolymer resulted.
45
The study of the initial rate as a function of the feed composition
made it possible to determine the relative value of the different pro¬
pagation reaction rate constants consistent with a mechanism by successive
and selective addition. However, participation of the CTC in a competing
mechanism with the above cannot be completely excluded.
In conclusion, a large portion of the evidence favors the partic¬
ipation of CTC in both the initiation and the propagation steps in the
alternating cyclocopolymerization. A complete explanation or mechanism
to fit all known data has not been reported. It is reasonable to say
that the reactivity, the complexation and the steric hindrance of the
comonomers all take part in the alternating tendency, rate, and the ring
size in cyclocopolymerization. The solvent and initiator may also
determine the rate profile of this copolymerization.
Statement of Problem
The objective of the present research has been to study cyclo¬
polymerization of donor 1,4-dienes with acceptor monoolefins and hope¬
fully learn more about the role of charge transfer complex (CTC) formed
between the comonomers in the cyclocopolymerization mechanism and to

23
develop a method to elucidate the structure of the cyclocopolymer by
various nuclear megnetic resonance spectroscopic methods. The following
research was conducted with this purpose in mind.
The Structure Analysis of Cyclopolymer of Divinyl Ether-Maleic Anhydride
(DVE-MAH) Comonomer Pair.
13
The ir, H-nmr, and C nmr spectroscopies are employed for this well
known 1:2 alternating copolymer. The 100 MHz and 300 MHz H-nmr spectra
were investigated in order to analyze the ring size and hopefully the
13
cis and trans content of the bicyclic ring. The C nmr spectrometer
should give simpler spectra and by comparing with literature values,
it should be possible to determine the ring size of the copolymer.
A partially deuterated divinyl ether (DDVE) was prepared which should
simplify the H-nmr spectral analysis. The 100 MHz and 300 MHz H-nmr
spectra of this DDVE-MAH copolymer should give more information on the
copolymer structure and help in the assignment of the respective signals
of the spectra which has been shown to be informative based on the liter-
16, 21
ature.
Rate Maximum Analysis
The study of the copolymer rate copolymerization rate as a function
of the feed composition made it possible to determine the participation
of CTC in the cyclocopolymerization. An irradiation at the wavelength
where only complex absorbed should confirm the initiation through CTC.
The participation of CTC in propagation can be supported by an analysis
of the proposed kinetic scheme. In order to compare the rate at the same
light intensity, the quantum yield was measured right after each irradia¬
tion. The structure of the cyclocopolymer of divinyl ether-furnaronitrile
13
monomer pair was determined by elemental analysis and C nmr spectroscopy.

CHAPTER II
THE STRUCTURE OF COPOLYMER OF DIVINYL ETHER-MALEIC ANHYDRIDE SYSTEM
Introduction
The field of cyclopolymerization has been explored extensively. A
variety of monomers containing two isolated double bonds have been found
to polymerize to form linear polymers containing cyclic units and little
or no residual unsaturation. High degrees of cyclization are obtained
when five- or six-membered rings can form and when all double bonds have
16
the same reactivity such as in diallylquaternary ammonium salts and
21
N-substituted diallylamines. The polymers of N,N-diallyl amines all
contained cis and trans-substituted pyrrolidine rings with ratio 5:1.
With a substituent on the 2-position such as N-methyl-N,N-bis(2-alkylallyl)-
amines, a complex spectra showed the presence of both pyrrolidine and
13
piperidine rings. The C nmr spectra of poly(diallyldimethylammonium)
chloride showed a predominant content of five-membered ring linked
mainly in a 3,4-cis configuration. Several works have studied the polymers
obtained from N-substituted dimethacrylamides. ^ In most cases f ive-
membered ring was found predominant with a small amount or no six-
membered ring.
The radical cyclization reaction involved in the polymerization has
been studied by means of model compounds. Julia reviewed the works
47 ...
on the cyclization of the 5-unsaturated radicals. Without substitution
on the radical carbon, only five-membered ring product was obtained.
With electronegative substituents on the radical carbon, the six-
membered ring product predominated.
24

25
Smith studied the cyclization of several 2-(allyloxy)ethyl radicals
48
with tributyltin hydride. The 2-allyloxy ethyl radical gave the tetra-
hydrofuran derivative as the only cyclic product. The 2-methyl- and
2-phenyl-allyloxyethyl radicals cyclized to give both five- and six-
membered ring products; in the latter radical the pyran derivative was
the predominant product.
Smith also found that with higher temperature the percentage of the
unfavored product increased; this indicated that the ring formation is
temperature dependent. It can be concluded that a five-membered ring is
energetically favored in the case of symmetrical non-conjugated dienes.
A steric effect would change the direction for radical attack on the
double bond. For unsymmetrical non-conjugated dienes with opposite
polarization on each double bond, the six-membered ring is predominant
as explained later. A head to tail cross-propagation has been found for
several oppositely polarized vinyl monomer pairs, such as maleic anhydride-
49
vinyl ether pairs, which introduced an alternating copolymer. The
cyclocopolymerization of DVE-MAH is similar to unsymmetrical non-conjugated
dienes, in which the cyclization step involves a favorable cross-propaga¬
tion reaction of oppositely polarized units.
It seemed worthwile, therefore, to investigate the structure of the
copolymer of DVE-MAH and to study the temperature dependence of the five-
and six-membered ring distribution in the copolymer.
Results and Discussion
Synthesis and Copolymerization of Bis(2,2-dideuteriovinyl)ether
Due to the small amount of materials available, the structures of
the products in each synthesis step were determined by ir and nmr spectro¬
scopy. A comparison of these spectra with spectra reported in the

26
literature and the spectra of the corresponding non-deuterated products
prepared by the same procedure confirmed the structures of the deuterated
compounds. In all cases the ir and nmr spectra of the non-deuterated
products were exactly the same as reported in the literature. Therefore,
the procedure for preparation of the non-deuterated ompounds were
applicable for the deuterated analogues.
A reaction scheme is shown in the following route:
LiAlD
4
THF
OH
r
0
?
\>
KOH
fciethanol
amine
0
D
\ Br
â– D
/D
/Sr
PBr
< 3
Pyridine
The 2,2,2',2'-tetradeuteriodiethylene glycol was prepared essentially
according to the method given by Bloomfield and Lee with only minor
50
modification. For complete reduction of anhydride, a prolonged reflux
period was required. In order to take the most advantage of lithium
alluminum tetradeuteride (LiAlD^), only a little excess of the deuteride
was used. The resulting glycol was soluble in water to a large extent,
hence, to isolate it from water solution was difficult. Even a salting
out process did not succeed. The reduction in ether solution was not

27
successful because of the low solubility of the anhydride. The reaction
seemed not to go at all. The best result was by using tetrahydrofuran
(THF) as solvent, with a small amount of water to destroy the aluminum
salt and release the glycol. The addition of 9 N sulfuric acid to dissolve
the aluminum salt did not improve the yield significantly. Therefore,
the complete dissolution of aluminum salt was not necessary. Water, fol¬
lowed by dilute acid was used to bring the glycol into THF solution.
The addition of excess anhydrous potassium carbonate, K^CO^, neutralized
the acid by evolution of carbon dioxide and absorbed water present in
the THF solution.
The diethylene glycol prepared by the same procedure showed exactly
the same ir and nmr spectra as reported in the literature. The ir
spectrum of 2,2,2',2'-tetradeuteriodiethylene glycol showed two
absorptions at 2220 and 2110 cm ^ of C-D stretching. The structure was
further confirmed by the nmr spectrum, in which a singlet was observed
instead of the multiplet in the spectrum of non-deuterated diethylene
glycol. The peak ratio of 1:2 instead of 1:4 (for diethylene glycol) also
indicated that the product obtained was tetradeuteriodiethylene glycol.
51
The bromination of deuterated ethylene glycol was straightforward.
The same method when applied to non-deuterated ethylene glycol gave a
product with exactly the same nmr and ir spectra as reported in the
literature. The ir spectrum of the resulting liquid for bis(2-bromo-
2,2-dideuterioethyl)ether showed an absorption at 2170 cm ^ which was
assigned to the C-D stretching. The nmr spectrum clearly confirmed the
structure with a singlet at 6 3.80 ppm. On the contrary, non-deuterated
dibromoethyl ether showed an AA'BB' multiplet at 6 3.70 ppm.
Finally the synthesis of bis(2,2-dideuteriovinyl)ether was prepared
by dehydrobromination from the corresponding dibromo compound. Only

28
the nmr spectrum was analyzed. The disappearance of ABX system which
showed up in the spectrum of divinyl ether, was evidence of the replace¬
ment of the four terminal hydrogens by deuteriums. A clear spectrum
was obtained by using larger sweepwidth. The constants for the hydrogen-
deuterium coupling (J ) was obtained by analyzing this spectrum.
By multiplying J by 6.5, the corresponding hydrogen coupling constants
HU
52
(J ) were obtained and were found to be close to the reported value.
HH
(Table IV).
Table IV
The Comparison Between J and J
HU HH
Coupling
JHD (H2)
Multiplied
Reported
by 6.5
JH„ trans
2
13.0
13.8
cis
1
6.5
6.2
The synthesized terminal deuterated divinyl ether (DDVE) was
copolymerized with MAH at 72°C in cyclohexanone by AIBN initiation.
The polymeric product was isolated and purified as a white powdery
solid which was soluble in acetone and dimethyl sulfoxide.
A series of copolymers of DVE and MAH were prepared at different
temperatures. The ir and nmr spectra were obtained and are discussed in
the next section.
The Structure of Copolymer
Infrared (ir) spectra. The ir spectra were shown in Fig. 1. The
two strong peaks at 1775 and 1855 cm ^ correspond to the reported
-1 53
absorption of succinic anhydride at 1782 and 1865 cm for symmetric

wavelength (cm ^)
Fig. 1 IR spectrum of the cooolymer of DYE-MAH prepared in xylene at 130 °C

30
and antisymmetric carbonyl stretching, respectively. The strong peaks
at 1230 and 950-920 cm 1 were assigned for the C-O-C absorptions for
cyclic anhydride unit. The strong peak at 1090 cm 1 with a shoulder
between 1060-1020 cm ^ was assigned for the C-O-C stretching for pyran
structure. The five-membered ring structure was ruled out by the fact
that the C-O-C stretching absorption for tetrahydrofuran is at 1062 cm .
The structure of the copolymer shown as structure X, with a 2,6-disubsti-
tuted tetrahydropyran ring and an anhydride unit on the 3,4-positions.
The 1:2 composition of DVE to MAH has been reported by Butler based on
the facts discussed in Chapter I. The spectra for 2,5-disubstituted
55
tetrahydrofuran has been reported by Mihailovic,et al. They observed
strong absorption at 1100 cm ^-for both cis and trans-2,5-dimethyl-
and diethyltetrahydrofuran.
The structure of the copolymer supported by ir spectra is likely
to have a six-membered ring. A conclusive result cannot be reached
because a suitable model compound for the comparison of ir spectra is
not available.
Hydrogen nuclear magnetic resonance (H-nmr) spectra.
The H-nmr spectra of polymers are usually broad. Therefore,

31
structure determination by H-nmr spectra is difficult. With the help
of the spectra of deuterated compounds and high resolution nmr spectro¬
scopy, it is possible to simplify the spectra and separate the overlapping
peaks. The 60 MHz nmr spectrum for DVE-MAH system copolymer was shown
in Fig. 2a. A four peak pattern was observed at 6 4.49, 4.06, 3.47 and
2.31 ppm with an area ratio of 1:1:1:2. The H-nmr spectrum of the
copolymer prepared with DDVE and MAH under the same polymerization
conditions exhibited the disappearance of the strong peak at 6 2.31 ppm
(Fig. 2b). Only the weak peaks corresponding to the residual solvent
were observed. Hence, the peak in the spectrum of nondeuterated copolymer
at 6 2.31 ppm was assigned for methylene protons which were 3 to the
ring oxygen. It has been reported that in the spectrum of the copolymer
prepared with DVE-3,4-dideuteromaleic anhydride (DMAH), the two peaks
centered at 6 3.47 and 6 4.06 ppm disappeared.'" Hence, these two
peaks are due to the four methine protons linked on the anhydride forms.
The peak at lower field was assigned to the proton on the ring, based on
the fact that the proton in a fixed position within a bicyclic ring will
experience a downfield shift caused by the electronegative oxygen nearby.
The methine protons next to oxygen are expected to experience a
deshielding effect to shift to lawer field at 6 4.49 ppm. The methine
protons next to oxygen have been reported to absorb between 6 4.00 and
57
6 3.30 ppm. Strong electron withdrawing effect of the two succinic
anhydride groups apparently shifts the methine proton to even lower field.
According to this analysis based on peak assignment and area inter-
gration, it can be concluded that the repeating unit of the copolymer has
two to one ratio of maleic anhydride to DVE which are arranged in an
exactly alternating manner. A random distribution of bicyclic and succinic

4.0 2.0 0
ppm (6)
Fig. 2 60 MHz nuclear magnetic resonance spectra of (a) DVE-MAH copolymer (b) DDVE-MAH
copolymer in acetone-dg

33
Table V
The Chemical
Shifts for the
Methine Protons
of DVE-MAH Copolymer
Spectra3
Next to 0
On the Ring
On the Backbone
Anhydride
Anhydride
60 MHzb
4.49
*+.06
3.47
60 MHzC
4.38-4.44
4.08
3.50
100 MHzC
4.18-4.44
3.88
2.96, 3.30
300 MHzb
4.29, 4.57
3.92, 4.14
3.01, 3.30
300 MHzd
4.34, 4. 46
4.67, 4.84
A6S
0.22
0.29-0.34
A6f
0.28-0.47
aAll chemical
shifts (5) are
in terms of ppm
relative to the
standard, TMS.
bNon-deuterated copolymer.
c
Deuterated copolymer of DOVE and MAH.
^Deuterated copolymer of DVE and DMAH-.
e
The chemical shift differences between the assigned cis and
trans methine protons.
^See reference 59.

34
anhydride units would give a more complex spectrum than the one reported
here.
The 60 MHz H-nmr spectrum is not able to distinguish between the
five- and six-membered ring due to the broad peaks caused by vicinal
protons and the different conformations and configurations.
For the purpose of distinguishing the cis and trans disubstitutions
and the five- and six-membered ring structures, a high resolution 100 MHz
H-nmr spectrum was performed for the copolymer of DDVE-MAH in acetone-d_
at 50°C (Fig. 3). The broad peak at 6 3.50 ppm with a shoulder at 6 3.16
ppm in 60 MHz spectrum was separated into peaks at 6 3.30 and 2.96 ppm.
The shoulder between 6 4.38 and 4.44 ppm was still unseparated and broad.
A 300 MHz nmr spectrum of DVE-MAH copolymer (Fig 4a) was performed by
58
Butler's group, in which a further separated pattern was observed.
The three peaks for methine proton groups are summarized in Table V.
Bode and Brockmann reported that the cis- and trans-2,3-disubsti-
tuted succinic anhydride showed 0.47-0.28 ppm difference in chemical
59
shift and the difference decreased with larger substitution. Therefore,
we can assign the methine groups of highest field with 0.34-0.29 ppm
splitting as the anhydride unit in the copolymer backbone. The one at
the lower field with less splitting (0.22 ppm) is then assigned as the
anhydride unit on the ring, which is deshielded by the neighboring pyran-
oxygen as discussed in the last section. In disubstituted succinic
anhydride, the chemical shift for the trans form is less than that for
cis form, 6 . ><5 , thus the four peaks in the MHz spectra for anhydride
cis trans r
protons can be assigned as: 3.01, 3.20, 3.92 and 4.14 for the protons on
trans-backbone, cis-backbone, trans-ring and cis-ring anhydride units,
respectively. On the backbone, the population of cis anhydride units

D D
0
0
CO
cn
7.0
6.0
5.0
4. 0
ppm (5)
3-0
i
2.0
Fig. 3 100 MHz nuclear magenetic resonance spectrum of DDVE-MAH copolymer

o
o
•o
5.0 4.0 3.0 2.0 1.0 0
ppm (ó)
Flg. 4 300 MHz nuclear magnetic resonance spectra of (a) DVE-MAH copolymer (b)
DVE-DMAH copolymer in acetone-dg

37
and the trans anhydride units are more or less the same. In contrast, more
trans form was present in the ring. The latter can be explained by the
possible bicyclic ring conformation, where a trans configuration is more
favorable. Butler and Guilbault prepared the copolymer of chloromaleic
anhydride with DVE having cyclized 1:1 composition with only DVE units
13
in the backbone. They investigated dehydrohalogenation of the copolymer.
From the ease with which the copolymer underwent dehydrohalogenation, they
suggested that the hydrogen and chlorine atoms on the anhydride unit in
the ring were in a trans configuration. However, H-nmr spectra showed
the presence of both cis and trans configurations with the latter in
favor.
By examination of the model of the bicyclic ring with large
substitutions on the carbons next to the oxygen, the six-membered ring
with chair form and trans junction is more favorable (trans isomer). In
this structure (XI), the two protons at the junction are in trans configura¬
tion. A chair form with cis junction is another alternative configuration
(cis isomer). However, the latter configuration (XII) experiences more
ring strain. On the contrary, a bicyclic ring with two five-membered
rings experiences much strain and only cis junction is possible, especially
when one of the rings is an anhydride unit (XIII). The heat of combustion
of trans bicyclo(3.3.0)octane is greater than the cis isomer by ca.
6 Kcal/mole.kO Thus, a trans junction pyran bicyclic structure with the
presence of cis isomer explains the analysis of 300 MHz nmr spectrum of
the DVE-MAH copolymer, based on the analysis of methine protons on the
anhydride units.
For a disbustituted cyclic ether, the chemical shift difference
between the cis and trans of the methine protons next to oxygen in the

38
literature have been reported to be between 0.11 and 0.51 ppm. ’ ’
In the case of the DVE-MAH copolymer, the methine proton signal was
split into two peaks by 0.28 ppm as shown on the 300 MHz spectrum. It
is reasonable to assign this group of peaks as a mixture of the two
configurations with more trans-isomer present because of the larger
area in the higher field corresponding to the cis form which was more
populated for a favorable trans isomer.
trans isomer
XI
This splitting pattern was more clearly observed in the 300 MHz
spectrum for the copolymer of DVE and DMAH (Fig. 4b). The two separated
methine proton (next to oxygen) peaks were further split into doublets.
The doublet indicated the nonequivalency of the two protons on each side
of the oxygen in the pyran ring. In contrast, the two protons for the
five-membered ring structure are more or less equivalent.
The methylene peaks on the higher field can be analyzed as a
mixture of two doublets; the larger doublet is assigned for trans isomer

39
which if further split by the fact that the methylene proton groups are not
equivalent. The splitting peak at the lower field with less intensity can
be assigned to the less populated cis isomer. In fused five-membered ring
structure, it is possible that the two methylene groups are linked in
0 3
either cis or trans configurations. However, a trans configuration
would introduce some strain in the bicyclic system with the two bulky sub¬
stitutions on the pseudo equatorial positions of the half-chair conforma-
64
tion. A cis configuration with the possible conformation is shown m
64
structure XIII. In this structure both the two methine hydrogens and
the two methylene groups on the 2- and 5-position are equivalent. There¬
fore, the splitting on Fig. 4b is most likely due to a chair form six-
membered ring with trans junction (trans isomer) with some cis isomer.
Further confirmation could be obtained by using bicyclic model compounds
and/or studying copolymers of additional monomers, e.g., CH2=CD0CD=CH9.
13
C Nmr Spectra
The line broadening inherent in H-nmr has severely limited the poten¬
tial of this technique for polymer structure analysis. In contrast, the
extended chemical shift range, the absence of significant dipolar line
13
broadening and the simplicity of proton decoupled C nmr spectra, in
which each carbon resonates as a singlet, makes these spectra extremely
useful for the study of polymers.
The spectrum of the copolymer of DVE-MAH was shown in Fig. 5a.
The spectrum consists of five major peak groups. From comparison with
published data the following general assignments can be made: the broad
peaks centered at 6 31.4 ppm with a shoulder at 5 35.8 ppm for methylene
carbon, the broad peak centered at 6 44.2 and 51.5 ppm with a shoulder
at 6 53.7 ppm for the carbon adjacent to the carbonyl groups, broad peak

COOH
o=c^>C=o
1=0
>0
(a)
171.7 78.7 51.5 Ü4.2 29.2
ppm (6)
1 ?
Fig. 5 JC nuclear magnetic resonance spectra of (a) DVE-MAH copolymer (b)
poly(maleic anhydride) (c) hydrolyzed DVE-MAH copolymer
ac x

41
centered at 6 78.7 ppm for methine carbon adjacent to the oxygen, the peaks
at 6 171.7 and 174.3 ppm for carbonyl carbons (Fig. 5a). The spectrum for
the copolymer hydrolyzed in Do0 does not change the pattern, but shifts
the peak to lower field (Fig. 5c). A comparison between the hydrolyzed
copolymer and the diacid model compound can be used for the assignment
of spectrum.
In a large series of compounds containing carbonyl groups, the
shielding is mainly influenced by the local electrons on the carbons.
The two carbonyl peaks suggest that two types of carbonyl groups are
present corresponding to the two anhydride carbonyls proposed by H-nmr
apectra, where one of the anhydride units is in the backbone and the other
forms the bicyclic ring. The two carbonyl carbons in each anhydride unit
are not expected to be greatly different from each other as far as the local
electron density is concerned. Therefore, the broadening of the peaks can
be explained either by the two different carbonyl carbons in each anhydride
unit or by the mixing of both cis and trans anhydride forms. A broader
peak is observed at the lower field, which-may indicate the equal mixing
of both the cis and trans forms.
The assignment of each carbonyl peak can be made by considering the
chemical shift difference between cis and trans configurations (A6 . ),
cis-trans
which would broaden the carbonyl peaks. The carbonyl carbon absorptions
of succinic anhydrides have been reported to be between 6 171.7 and 175.3
ppm. ^ The C nmr spectrum for a dl-meso mixture of 2,3-dimethyl succinic
acid is shown in Fig. 6. The chemical shift differences between the
two carbonyl carbons, the two methine carbons and the two methyl carbons
are 0.7, 0.9 and 1.4 ppm respectively. This small chemical shift differ¬
ence for carbonyl carbons between the isomers of dimethyl succinic anhydride

177-8 41.2 29-2 13-0
ppm (ó)
Fig. 6 13
acid
C nuclear magnetic resonance spectrum of 2,3-dimethyl succinic

43
is expected for the carbonyl carbon peaks for the copolymer where only
a broadening effect is observed. The peak at the lowest field can be
thus assigned for the carbonyl carbons on the backbone because it is
broader than the other carbonyl carbon peak. This is reasonable because
the sharper peak then assigned for the anhydride on the ring, can be
explained by the less population of cis form. This sharper peak is
broadened by the hydrolysis of the copolymer as expected by the loss
of the rigidity of the bicyclic structure.
A comparison between the spectrum of the copolymer and poly(maleic
58
anhydride)(Fig. 5b) showed clearly that the broader carbonyl carbon peak
can be assigned to the anhydride unit on the backbone, and also, the methine
carbon peak at the higher field is for the anhydride unit on the backbone.
On the other hand, the two peaks at 51.5 and 53.7 ppm with a difference of
2.2 ppm can be assigned for the two non-equivalent methine carbons on the
six membered ring by comparing with the 3- and y-carbons on thetetra-
hydropyran which has a difference of 2.8 ppm.
The peaks at the lower field of the methine carbon region (6 51.5-
55.5 ppm) are then assigned to the methine carbons on the ring anhydride
unit; the larger peak from trans isomer and the weak peak from the smaller
contribution of cis isomer. The methylene carbon peak is assigned to
the trans isomer which is broadened by the non-equivalency of the two
methylene groups in the copolymer. The shoulder at 6 35.8 ppm can be
assigned for the methylene carbons of the less populated cis isomer.
By comparing the methine carbons of the copolymer with poly-
id iallyldimethylammonium)chloride, (XIV), 1,1,3,5-tetramethylpiperidinium
iodide, (XV), and 1,1,3,4-tetramethylpyrrolidinium iodide, (XVI), in
Table VI, the chemical shift difference between the cis- and trans-
methine carbons in the copolymer is closer to the six-membered ring

44
structure than the five-membered
ring structure.
16
Table VI
Chemical Shits Differences Between cis and trans Disubstituted
Vincinal Carbons in l^C nmr Spectra
Structure
A6 .
cis-trans
On the Backbone
(ppm)
On the Ring
Hydrolized
Copolymer
of DVE-MAH
<1
2.2
2,3-Dimethyl
Succinic Acid
0.9 '
-
XIV
4.5-5.0
XV
1.8
XVI
6.2
Kunitake and Tsukino suggested an all five-membered ring structure
for the copolymer of DVE-MAH system by the fact that a highly symmetric
structure is involved, the two singlets observed for the carbonyl carbons

45
and the comparison of the estimated chemical shift values to the
experimental values. This suggestion can be argued against by (1)
in the spectrum of the copolymer, the difference between the two
carbonyl carbons in each anhydride unit is so small that a splitting
causes only the broadening of the peaks. Hence, the absence of the
doublet for each peak cannot be explained as the absence of the non¬
equivalent carbonyl carbons, such as those in the six-membered ring
in the copolymer. (2) The analysis of H-nmr spectra was best represent¬
ed by six-membered ring copolymer structure, although the unlikely
mixing of both five- and six-membered ring structures cannot be ruled
out completely.
The Temperature Dependence on the Copolymer Structure
Due to the possibility of the mixing of both six- and five-
membered ring structures in the copolymer, temperature effect experi¬
ments were carried out to investigate the temperature dependence on the
contribution of these two structures.
The copolymers were prepared at different temperatures, 25°, 72°,
100°, and 130°C. The results are shown in the experimental section. The
spectra for each copolymer are shown in Fig. 7. No major change was
observed. The small side peak a-t 6 35.8 and 51.5 ppm both gradually
disappeared or flattened with the decreasing of temperature. This small
change cannot be considered to be real because of the accidental experi¬
mental errors such as lower resolution and the different concentrations of
the samples. Even the different solvents used for preparation should be
considered.
It is reasonable to conclude that no significant change of structure
caused by the temperature effect is obtained. This fact can be explained

46
171-7 78.7 51.544.2 29.2
ppm (6)
13
Fig. 7 C nuclear magnetic resonance spectra of DVE
MAH copolymer prepared at (a) 130, (b) 100, (c) 72,
(d) 25 °C

47
by the production of only one energetically favored product which is
the six-membered ring structure as revealed by all the spectroscopic
analysis.
The Mechanism of Cyclization
The structure and temperature analysis concluded that a highly
energetically favored six-membered ring copolymer was the product of
the copolymerization of DVE-MAH system. In cyclization of the sym¬
metric non-conjugated dienes, the ring size is controlled by the
entropy effect of the two ring formation processes. A five-membered
ring product is favored because of the less entropy change involved.
With substitution, a sterically favored six-membered ring formation
is able to compete with the former process. Also, the substitution on
the radical carbon of the uncyclized radical makes both the processes
higher activiation energies and hence, less selective. At the extreme,
with two electronegative and steric substituents on the radical carbon,
47
a six-membered ring formation will be highly favored.
The energetical factor is much different for a cyclization involving
non-symmetric non-conjugated dienes such as the cyclization in the
cyclocopolymerization of DVE-MAH system. During the cyclization step,
the vinyloxy double bond is attacked by a radical on the anhydride unit:
0.
0

48
This process can be shown to be highly enthalpy-controlled by
considering the closer energy gap between the HOMO of vinyloxy double
bond and the singly occupied molecular orbital (SOMO) of the anhydride
radical than that for the corresponding symmetrical diene cyclization.
— LUMO
LUMO
SOMO
alkyl
radical
HOMO
double
bond
stabilized
radical
SOMO
HOMO
destablized
double bond
The HOMO of the vinyloxy double bond is polarized to have higher
0 y
orbital density on the terminal position. Therefore, a fast radical
addition on the terminal carbon of the double bond leads to a six-
membered ring radical. A copolymer with six-membered ring structure X
is thus obtained.
As discussed in chapter I, a charge transfer complex was proposed to
explain the fast cyclization. The charge transfer complex can be applied
here with the help of HOMO-LUMO concept to predict the ring structure
of the cyclization step.
The Milliken theory of overlapping and orientation principle predicts
that stabilization in the molecular complex formation should essentially

49
be determined by the overlap of the donor HOMO and the acceptor LUMO.^
In the examination of ir and Raman spectra of DVE, Claugue and Danti
69
proposed the presence of two rotational isomers. The more stable isomer
has Cg symmetry, in which the two vinyl groups, although coplanar are
non-equivalent. Hirose and Curl examined the microwave spectrum and
assigned the conformen. ^ They found a small nonplanarity caused
by H-H repulsion between the 3-hydrogen of the cis vinyl group and the
a-hydrogen of the trans vinyl group-(XVIII).
H
cis-trans
The charge distributions in vinyl ether and vinyl methyl ether were
6 7
calculated by CNDO/2 method by Fueno , et al. It was found that a large
electron density was on the terminal position as in sturctures XIX and
XX.
XIX
XX

50
This charge density of orbital actually describes the orbital density of
the HOMO of DVE. The LUMO of MAH has been described by Fukui as
structure XXI with higher orbital densities on the double bond carbons,
71
but antisymmetrical to the plane of symmetry of this compound.
Therefore the most stable conformation for a DVE-MAH complex can
be expected as XXII, based on the conformer structure of DVE and the
molecular densities of both comonomers.
0
When this complex is initiated by a radical, a six-membered ring
radical will be formed concerted (Path a) or stepwise through an anhydride
radical addition on the terminal carbon of the vinyloxy unit (path b).
This complexation would reduce the energy gap between the complex and
the propagating anhydride radical, thus, a radical addition on the
complex occurred and the reaction is supposed to be fast. This special

51
complexation and/or interaction would significantly reduce the activa¬
tion enthalpy for the formation of six-membered ring. In the range
of the temperature sutdied, a five-membered ring formation cannot compete
with it at all, which explains the temperature independence on the
structure of the cyclocopolymerization.
In conclusion, on the mechanism of the cyclization and copolymer¬
ization of DVE-MAH system, it is reasonable to be stated as follows.
(1) The intramolecular cyclization is favored over the intermolecular
addition due to the lower entropy change of the former process than the
latter one. This explains the high degree of cyclization.
(2) The entropy preference cannot be explained on the base of activation
energies and the statistical probability. A preorientation either
through the delocalization of the radical with the intramolecular double
bond or the formation of complex is proposed.
(3) This preorientation would lead to a six-membered ring structure
by a favorable energy factor based on the HOMO orbital density of DVE.
For a symmetrical nonconjugated diene the five-membered ring cyclization
is favored by the entropy factor.
(4) A faster rate of this cyclocopolymerization than the copolymerization
of the corresponding monoolefin -pairs can be explained by the closer
energy of the anhydride radical to the complex.
The proposed cyclization mechanism can be applied on other comonomer
pairs and is worthy of further investigation.

CHAPTER III
THE COPOLYMERIZATION OF DIVINYL ETHER-FUMARONITRILE
Introduction
It was pointed out in Chapter 1 that a donor-acceptor pair of
comonomers could produce alternating copolymer through a charge transfer
complex (CTC). In the cyclocopolymerization of donor 1,4-dienes with
acceptor monoolefins, alternating cyclocopolymers having 1:2 composi¬
tion were obtained for several systems. The participation of CTC formed
between the donor and acceptor was proposed to explain the alternating
copolymerization. However, it has been known for sometime that the
compositions for the copolymers are 1:2 while the stoichiometry of the
CTC are always 1:1. An alternating copolymerization of a CTC and a free
monoolefin was proposed as an explanation. It has been shown that
when an acceptor monoolefin is highly sterically hindered and hence much
less reactive, according to the above explanation, a 1:1 cyclocopolymer
14 43
was obtained apparently through the homopolymerization of CTC. ’
With a less sterically hindered monoolefin and less reactive monoolefin
it is possible to form a cyclocopolymer with composition between 1:1
and 1:2. The cyclocopolymer of DVE-FN has been reported having the FN
content between 0.55 and 0.63 mole fraction which is in the range of
32
0.50-0.67 for the 1:1 and 1:2 composition. With dilution, less FN
content was reported and a contribution of either homopolymer structure
of DVE and/or 1:1 comonomer unit in addition to the regular 1:2
37
comonomer unit was proposed as an explanation.
52

53
A further structural analysis and the study of the participation of
CTC in the copolymerization are discussed in this chapter
Results and Discussion
Study of the DVE-FN complex in Acetonitrile
On the basis that the complex formed between DVE and FN may
participate in the mechanism of initiation of the photocopolymerization
in acetonitrile solution, the characteristics of the complex were
studied in the same solvent. The existence of the complex was estab¬
lished by UV spectrophotometry. A mixture of 0.6 m/1 of DVE and 0.6 m/1
of FN showed a large absorption between 250 nm and 350 nm (Fig. 8)
although a distinguishable new absorption band was not observed.
This large enhancement of absorption indicated the presence of complex.
A 1:1 stoichiometry was determined by the continuous variation method
72 '
at 300 nm - (Fig. 9). The maximum of the absorption for different
compositions of DVE and FN, while their total concentration was kept
constant was found for equimolar composition.
The charge transfer complex of an acceptor-donor pair is in
equilibrium with the free components. The charge transfer complex exists
in resonance between the no-bond state and the dative state; thus the
wave function of the charge"transfer complex (V ) can be expressed as a
linear combination of wave functions of the no bond state [T(D,A)] and
the dative [T(A-, D*) ] (Equation 1 and 2).
K
A + D —^ [(A,D) + (A•, üt)] (Eq. 17)
Yct = aT*(A,D) + b?-(A7, D?)
(Eq. 18)

Absorbance
Wavelength (nm)
Fig. 8 The absorption of the complex of DVE-FN in acetonitrile (a)
0.6 m/1 of DVE, (b) 0.6 m/1 of FN, (c) (DVE) = (FN) = 0.6 m/1.

Absorbance
Fig. 9 The determination of the stoichiometry of the DVE-FN complex in
acetonitrile by continuous variation method at 300 nm (DVE) + (FN) =
0.60 ± 0.03 m/1

56
2 2
For a regular loose complex, a >>b in the ground state of the com¬
plex. The dative structure corresponds to an ionic-radical-like pair.
There must be also an excited state (T^) which can be called a charge
73
transfer state given by
Â¥ct * b T0(A,D) + a T,(A-,D-)
(Eq. 19)
*2 *2
The excited state is mostly dative (a »b ); excitation of an electron
from ¥ to ¥ essentially amounts to the transfer of an electron from
donor to acceptor. Spectroscopic absorption would occur with this excita¬
tion (charge transfer absorption). A charge transfer absorption is
possible for any pair of molecules if in contact, even if they do not
form a stable complex.
A complete absorption spectrum of a complex consists of absorption
to (1) locally excited state (states of donor or of acceptor, more or
less but usually not greatly modified in the complex.) (2) charge
transfer states [(¥ in Eq. 19, and other charge transfer states includ¬
ing the excited dative structures, for example T(D+ ,A*)].
The equilibrium constant (K ) of the complex can be measured by
using Merrifield and Phillips method
A,
Ac
74
= -K A. + K (A) £.
(D)0 c Ac c ° Ac
(Eq. 20)
(D)0 - The initial donor concentration
(A)0 = The initial acceptor concentration
A. = Absorbance of complex at certain wavelength
Ac
= The equilibrium constant for the formation of weak complex
- (Complex)/(D)(A)

57
e. = The extinction coefficient of the complex at wavelength.
AC
For a series of solutions containing different concentrations of
DVE but with constant concentration of FN, with condition (DVE)>>(FN),
a plot /(DVE) against should be linear. From the gradient of the
line, Kc may be evaluated directly without recourse to an extrapolated
intercept. The absorption of DVE-FN complex and the resulting plot in
acetonitrile are shown in Fig. 10 and Table VII. The equilibrium con¬
stant was small (K = 0.10) and cannot be evaluated exactly, but it is
compatible with the equilibrium constant measured in methanol solution
(K = 0.12 to 0.20).
c
Table VII
Determination of Equilibrium Constant of FN-DVE in
Acetonitrile with Constant FN Concentration (0.00101 m/1)
(D)o
m/c
280
nm
300
nm
A
A/(D)q
A
A/(D)q
0.846
0.031
0.0520
0.013
0.0154
1.69
0.081
0.0479
0.029
0.0172
2.12
0.100
0.0472
0.031
0.0146
2.96
0.137
0.0463
0.042
0.0142
3.81
0.152
0.0399
0.040
0.0105
K
0.
09
0.11
c
The equilibrium constant of complexation can be determined by nmr
75
spectroscopy using the Hanna-Ashbaugh equation. The attempted nmr
method failed because one of the quartet absorptions of the ot-vinyl

Absorbance
260 280 300 350
Wavelength (nm)
Fig. 10 Charge transfer absorption of DVE-FN complex in acetonitrile

59
proton of DVE covered the peak of the protons of FN, whose chemical shift
was to be used to determine the equilibrium constant in acetonitrile.
The Structure of the Complex
The spectroscopic determination of stoichiometry and the equilibrium
constant of the charge transfer complexes of monoolefins with 1,4-dienes
37
have been thoroughly discussed previously. Amazingly, in all cases
studied the stoichiometry is 1:1. The structure of the complex has not
been established. Either one or both of the double bonds of the 1,4-diene
can be complexed with acceptor. Take DVE and FN as an example:
The first structure is not likely because with a free double bond
available, a second acceptor would be complexed more or less as easily
as the first acceptor molecule to form a 1:2 complex.
1:2 complex
As pointed out in Chapter II, considering the conformation of DVE
and the orbital densities of both HOMO of DVE and LUMO of acceptor, the
most stable conformation of the complex can be predicted as structure XXIII.
The proposed relation between no bond state and the dative state of this
complex is shown in equation 21.

60
CN
(Eq. 21)
Dative state
No bond state
At ground state the complex can be represented by the no bond state,
the excited state (CTC);'; after the absorption of appropriate light energy
can be represented by dative state. In general an excited state would be
radiationlessly deactivated without associating with external environment
In the case of (CTC)*, the state is so polar that the environmental polar
molecules (acceptor, donor and ground state complex) would participate in
its deactivation processes.
At 236 nm, while most of the light is absorbed by the free monomers
to form excited monomers, the excited state of DVE would interact with
the ground state of FN to form an exciplex which possesses higher energy
than the previously mentioned c rge transfer state [(CTC);’: formed by
1 0
irradiation at 300 nm where only the complex absorbs]. The exciplex is
polar enough to be deactivated with the participation of ground state
molecules. (Scheme I)

61
(OVE _ no 500JÜU. (OVE -» FN)* Sg&Sggfift» DVE t FN
molecules
236 nm^. í: FN^ (DVE*.FN) S2L™5ÍI¿2Í, DVE t FN
molecules
environmental
molecules
DVE
Scheme I
The Structure of the Copolymer of DVE-FN System
13
Ir and H-nmr spectra. The ir, H-nmr and C nmr spectra were record¬
ed for the copolymers prepared by irradiation at 300 nm, 236 nm and with
AIBN, in acetonitrile with feed composition f = 0.5 (Table VIII).
Table VIII
Comparison of Copolymers Initiated
Methods in Acetonitrile
by Different
Feed Composition
Initiation
Conversion
m *
(FN)
(DVE)
*
0.6 m/1
0.6 m/1
AIBN
44%
0.408
0.6 m/1
0.6 m/1
236 nm
40%
0.402
0.6 m/1
0.6 m/1
300 nm
55%
0.486
*Molar fraction of DVE in copolymer calculated from nitrogen
and carbon content

62
All the copolymers showed the same characteristics in ir and H-nmr
spectra, thus indicating that the same propagation processes are employed
for all methods of initiation.
The copolymers absorbed in the infrared region: 2250 cm ^ (s)
(CN stretching) and near 1100 cm ^ (broad)(ether group), showning the
existence of the comonomer units. There was also the presence of
-1 32
vinyloxy double bond absorption at 1630 cm . It has been observed
that only a small amount of residual unsaturation (from 2.0 to 3.5%) was
in the copolymer prepared by the initiation of AIBN in dimethylformamide.
The infrared spectra of copolymers initiated by light at both 236 nm
and 300 nm had the same characteristics as the one initiated by AIBN in
acetonitrile (Fig. 11). It is reasonable to assume that the same small
amount of unsaturation was in the photocopolymers. This conclusion was
also shown in the H-nmr spectra (Fig. 12) where no absorption contributed
by vinyloxy double bond was observed. Therefore, there is no significant
contribution of the structures with the pendant vinyl group in the copoly¬
mer.
X
XXIV
CN
The composition of the copolymer. The composition of the copolymers
has been determined over a wide range of monomer feed compositions. The
copolymers of DVE-FN are quite hygroscopic. The elemental analysis showed
higher hydrogen and oxygen weight percentages than calculated from nitrogen

63
Fig. 12 60 MHz nuclear magnetic resonance
spectra of the DVE-FN copolymer initiated
(a) at 300 nm, (b) at 236 nm, (c) by AIBN

64
and carbon. The nitrogen content is only from FN monomer, the calculation
of the number of nitrogen atoms permitted the determination of the
copolymer composition.
no. of moles of FN = no. of moles of nitrogen atoms/2
no. of moles of DVE
no. of moles of carbon atoms - no. of moles
of FN x 4
m
d
the molar fraction of DVE in the copolymer
no. of moles of FN
no. of moles of DVE + no. of moles of FN
The results are shown in Table IX and Fig. 13.
Table IX
The Compositions of Copolymers Prepared in Acetonitrile at
Room Temperature within 10% Conversion
Concentration (m/1)
(FN) (DVE)
300 mn
c
m d
236 nm
md
0.4
1.6
0.80
0.410
0.408
0.8
1.2
0.60
0.372
0.436
0.6
0.6
0.50
0.4863
0.402a
1.2
0.8
0.40
0.412
0.400
1.6
0.4
0.20
0.351
0.436
Average
0.406
0.416
aMore than 40% conversion.
Molar fraction of DVE in feed,
c
Molar fraction of DVE in copolymer calculated from
nitrogen and carbon weight percentage.

0.7
0.6
6o 0.5
0.4
0.3
0.2
0.1
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
fd
Fig. 13 The compositions of the DVE-FN copolymer initiated at (a) at
236 nm, (b) at 300 nm.
CD
CJl

66
There was no apparent trend for compositions of copolymer. The
copolymers irradiated at different wavelengths have similar compositions
(average m^ = 0.406-0.416). It indicated that the same propagation process
was employed for both wavelengths. For a typical 1:2 copolymer and a 1:1
copolymer, is 0.33 and 0.50 respectively. The compositions of both
copolymers fell in the range from 0.351 to 0.486 within a wide range of
feed compositions. Together with the spectroscopic data this is the basis
of assuming a copolymer containing both the 1:1 and 1:2 copolymer structures
XXIV. Note that is is not necessarily a block copolymer in the sense of
1:1 and 1:2 monomer combinations. The 1:1 repeating unit has been found
77
m the copolymerization of p-dioxene-MAH, DVE-DMTHNQ and DVE-THNQ
43 . .
systems, m which the homopolymerization of a 1:1 CTC was considered.
CN
XXV
When the reaction time of copolymerization was long enough so that
the reaction was almost completed, it was observed that the yield at 236 nm
for large excess of DVE in feed composition was more than the corresponding
theoretical maximum of conversion of a perfect 1:2 copolymer but less than
or close to the 1:1 copolymer (Table X). At 300 nm the yield was less
than the theoretical 1:2 copolymer.
The excess yield at 236 nm can be explained by the involvement of
either the homopolymerized DVE or the 1:1 copolymer structure in the 1:2
overall copolymer structure. When FN is about used up at the end of the

67
reaction, homopolymerization of DVE has a chance to compete with the
copolymerization. The fraction of DVE in copolymer (m^) supports the
involvement of homopolymerization of DVE. What is important is that the
close value of rn^ at both 300 nm and 236 nm (m^ = 0.56+0.03) indicating
that the involvement of homopolymerization is in the propagation process
instead of the initiation process, in other words, in the early stage
of the copolymerization, the homopolymerization is not involved.
Table X
The Limiting Yield of Copolymerization with
Excess DVE in Feed Composition
Wavelength
(nm)
Feed
Composition
FN%
Yield
(mg)
Theoretical
1:2 Copolymer
Yield (mg)*3
1:1 Copolymer
a, c
md
300
2
24.8
32.5
—
—
5
40.1
49.7
—
--
10
115.7
135.1
—
0.54
236
1
25.7
24.8
32.5
0.59
2
45.1
32.5
42.5
--
5
' 78.9
57.3
75.0
0.52
10
161.0
143.7
188.2
0.57
aThe fraction of DVE in copolymer calculated from nitrogen and carbon
^content.
Based on the reacted amount of FN.
c
Average = 0.56.
The different initiating wavelength would finally form the same
intermediate or intermediates which initiates the same propagating radicals.
13
The structure of this copolymer can be further confirmed by C nmr spectro¬
scopy.

68
13 13
The C nmr spectra. The C nmr spectrum of the copolymer is
shown in Fig. 14. The four peaks at 6 118.5, 117.9, 116.6, and 116.1
ppm from TMS in the CN region supports the six-membered ring structure
where two of them correspond to the two unsymmetrical CN's on the ring
and the other two correspond to the CN's on the skeleton.
It was pointed out in Chapter II that the small difference between
the two carbonyl carbons would only cause a broadening of the peak
instead of splitting it. This assumption can be applied here that the
doublet of each CN peak does not indicate two non-equivalent CN's in
the ring or on the backbone. The chemical shift difference (0.5-0.6 ppm)
between each peak in the doublet is close to the difference of the carbonyl
peaks of dl-meso mixture of 2,3-dimethyl succinic acid (0.9 ppm). We
can assign the doublet as the consequence of the mixture of cis- and trans-
dicyano substitutions on each fumaronitrile unit. These assignments will
lead to a reasonable conclusion that in backbone, cis- and trans-disubstitu
tions are more or less equally populated, by considering the equal
intensities of the doublets as shown on the peaks at 6 117.9 and 118.5 ppm.
The CN's at 6 116.6 and 116.1 ppm indicated the different populations of
cis- and trans-disubstitutions, which are possible during the ring formation
It is difficult to assign the chemical chifts of the CN groups
without comparing with model compounds, but at least a copolymer with
the 1:1 and 1:2 copolymer composition is consistent with the spectra.
The two C-O-C peaks in the C-O-C region indicated the existence of
13
two different C-O-C linkages in the copolymer. Comparing the C nmr
spectra of homopolymers of DVE with the copolymers enabled us to clarify
the exclusion of homopolymer structure in the copolymer.
(Table XI)

69
236 nm, (b) by AIBN, (c) at 300 'nm.

70
Table XI
13
Comparison of C nmr Spectra Between Homopolymer of DVE and
the Copolymer of DVE and FN
Material
Chemical Shift No. of CN Substitutions Calculated
(ppm from TMS) on C*'s total shift
of C"'s (ppm)
Homopolymer
XXVIII 82.3, 83.4, 151.1
XXIX 84.2
XXX 77.8
Copolymer
XXVI
79.6
a, 0;
3,
l;
Y,
2
+11
XXVII
76.7
a, 0;
6,
i;
Y.
1
+ 10
'••The special carbon in consideration.
XXIX
/
XXVI
XXVII

71
Comparing the C*'s in trimethyleneglycol (two oxygens are three carbons
apart) with pentamethyleneglycol (two oxygens are five carbons apart),
there is a 2.9 ppm difference in chemical shift due to the distance of
79
the two oxygens. The 2.9 ppm difference of the two C-O-C absorption
in the copolymer can then be explained by comparison between the C*'s
in structure XXVII and then XXVI.
59.2 ppm
62.1 ppm
In conclusion, at low conversion, the copolymer contained a mixture
of structures XXVI and XXVII, a small amount of residual unsaturation and
probably some homopolymer structure which can be neglected for kinetic
consideration. The average m^ = 0.41 corresponding to a 56% of structure
XXVII. This ratio of structure XXVI to structure XXVII was reflected
13
by the almost equal intensity of the two C-O-C absorption in C nmr
spectra.
To distinguish between pure five- and six-membered ring structures
is very difficult because of the lack of information. As discussed
in Chapter II, it is unlikely to have a mixture of both six- and five-
membered rings structures in the copolymer because of the simplicity of
the spectrum. Furthermore, a favorable conformation of the complex and
the orientation of the cyclization makes the six-membered ring structure
more possible.

72
Quantum Yield Study
Quantum yields for formation of copolymer were measured in aceto¬
nitrile and at different wavelengths. The intensities are different at
different wavelengths for monochromatic light source. It will be pos¬
sible to compare the quantum yields at different wavelengths by knowing
the dependence of intensity on quantum yield.
The data obtained for 0.6 m/1 FN and 0.6 m/1 DVE in acetonitrile
at 300 nm showed small dependence on light intensities. The intensity
was altered by using different slits.
The quantum yields were not exactly independent of the intensity
for nonequal molar solutions with 0.47 m/1 of FN and 0.71 m/1 of DVE
in acetonitrile at 300 nm. The intensities were altered either by
the different slits or with a copper screen in front of the sample tube
in this case. Also, the quantum yields were changed with different
intensities at 236 nm, with 0.6 m/1 of DVE and 0.6 m/1 of FN. The data
of the light intensity dependence on qauntum yeild and rate are listed
in Table XII.
The linear dependence of intensity on quantum yield are shown in
Table XIII. The linear correlation coefficients were close to one
indicating that the equations can be used for comparing the quantum
yields at the same intensity for different wavelengths. The results are
shown in Table XIV. Apparently the quantum yield at 236 nm is larger
than at 300 nm.
Ferree and Butler observed that the quantum yield was constant or
declined slightly as the wavelengths decreased, until part of the divinyl
ether band is excited at 236 nm, at which point the quantum yield in-
5 8
creased drastically. This fact suggests that only excitation in either

Table XII
The Light Intensity Dependence on Quantum Yield and Rate in
Acetonitrile at Room Temperature
Concentration (m/1)
DVE FN
Wavelength
(nm)
Light Intensity
photons/sec
Quantum
Yield
Conversion
O.
O
Rate
mg/min
0.6 0.6
300± 3.2
3.48 X 10-15
0.062
2
0.098
300± 9.6
2.37 X 1016
0.049
4
0.54
300±12.8
3.29 X 1016
0.059
11
0.88
300116.0
5.61 X 1016
0.052
5
1.31
0.47 0.71
300112.8
4.41 X 1016
0.038
1
0.761
• 3001 6.4
1.41 X 1016
0. 044
2
0.285
3001 6.4
5.7 X 1015
0.054
2
0.140
3001 6.4
0.77 X 1015
0.079
2
0.026
0.6 0.6
236122.4
14
115 X 10
0.048
3
0.25
236116.0
73
0.051
2
0.17
236116.03
59
0.056
2
0.15
2361 9.6
25.5
0.068
2
0.079
2361 9.6a
7.4
0.095
2
0.032
2361 6.4
7.8
0.102
2
0.036
2361 3.2
3.4
0.126
—
0.019
aWith a copper screen
^With a copper screen
in front of
fold twice
the sample tube.
in front of the sample
tube.

Table XIII
The Linear Relations of Intensity (I) to the Quantum Yields ($) and Rates
Wavelength Concentration (m/1) Linear Dependence Equations3 Correlation
(nm)
FN
DVE
Coefficient
300
0.6
0.6
log($ x 102) =
-0.06 log(I x 10"15)- 1.8
2
log(rate x 10 )
= -0.457 + 0.94 log(I x 10"14)
0.99
300
0.47
0..71
, 2
log($ x 10 ) =
-0.18 log(I x 10"14)+ 1.5
0.98
2
log(rate x 10 )
= -0.293 + 0.821 log(I x 10~14)
1.00
236
0.6
0.6
2
log($ x 10 ) = â– 
-14
-0.271 log(I x 10 )+ 1.23
0.99
2
log(rate x 10 )
= -0.104 + 0.72 log(I x 10"14)
0.99
Rate is m
mg/min. I
is in
photons/sec.

75
the charge transfer complex absorption band or the divinyl ether
absorption band leads to initiation of copolymerization.
Table XIV
Comparison of Quantum Yield and Rate at 236 nm and 300 nm
Compound
Concentration
Wavelength
(nm)
Intensity
Photons/sec
Quantum
Yield
Rate
mg/min.
FN
0.47 m/1
236
14
8.86 x 10
0.118
0.479
DVE
0.71 m/1
300
14
8.86 x 10
0.076a
0.304a
Calculated from equations
in Table XIII.
\
It has been suggested that an exciplex was responsible for the
copolymerization while no ground state charge transfer complex was
7 6
observed, such as the photocopolymerization of vinylcarbazol and
acrylonitrile. Since at 236 nm the only effective photoabsorbing
species was DVE, the initiation process must proceed via the excited
state of DVE. Although there was no evidence of exciplex of DVE and FN,
no significant homopolymerization was obtained with DVE alone, this
fact indicating that the excited DVE initiated copolymerization possibly
through the interaction with the ground state of FN.
DVE
236 nm
>
(DVE)*
(DVE)* + FN » (DVE* -> FN)
exciplex

76
At 300 nm the photoabsorbing species was complex, therefore the
initiation process proceeded via the excited state of the complex.
DVE + FN * (DVE - FN) —— (DVE+FN)*
< 300 nm
At both wavelengths, the excited species dissociated into initia¬
ting radicals. Although the initiating radicals have not been identified
they could be a paired cationic radical and anionic radical.
kd •
(DVE*FM)* - > 2R*
1
k'd
(DVE*-*FN) 2R-
The ionic radicals initiated the copolymerization through free radical
processes because both air and a small amount of diphenylpicryl-
hydrazyl free radical (DPPH) retarded the reaction.
R- + (DVE
A small amount of FN (1%) did not initiate the homopolymerization of large
excess DVE (99%) to a significant extent. This indicated that the divinyl
ether radical formation can be excluded at least in the early stages of
the copolymerization.
R. + =-0-=

77
The initiation through free fumaronitrile cannot be excluded but probably
is not able to compete with the low energy pathway of the complex
initiation process.
At 300 nm the light was totally absorbed by the complex for the
solution of 1.2 m/1 and of FN and 1.2 m/1 of DVE.
FN + DVE ^ > (DVE FN) (DVE
c c
2R*
(DVE —> FN)* is the excited complex.
(DVE
FN)*
(DVE)
(FN)
(DVE-^ FN)
Ground state molecules
Scheme II
I = The light intensity absorbed by the complex.
= I ks (light intensity absorbed by actinometer).
= The quantum yield with only radiation deactivation considered.
The excited complex may be deactivated by collision processes.
As discussed before the exact structure of the excited state is not
known, but it may still be very polar and very likely to be deactivated
by the polar monomers and the ground state complex. The radiationless
deactivation process may be proposed as in Scheme II.
The rate of formation of the primary radicals (R*) can be derived by
applying the steady state assumption and assuming that the radiationless
rates of the deactivation of excited complex is proportional to the total
concentration of monomers, (T).

78
-d(DVE
FN) *
dt
rl
k ,(T)(DVE
rl
TN)*
Therefore,
d(DVE -> FN)-;
dt
I $ (DVE FN)*(k, + k , (T)) = 0
c c d rl
From Scheme II
R. = k (DVE FN)* = (k I $ )/(k, + K ,(T))
id d c c d rl
At 236 nm the complex absorbed insignificantly but DVE absorbed part
of the light, Ij = labs^diDVE)» and is responsible for the initiation
through the following equation.
DVE
Vd
DVE*
FN
^ (DVE*
FN)
2R*
df
rl
radiationless deactivation
is the quantum yield with only radiation deactivation considered.
In the same way as proposed at 300 nm, the rate of formation of the
primary radicals (R*) can be derived by assuming the rate of the
d(DVE* -> FN)
deactivation of exciplex, (â– 
dt
) , is proportional
to the total concentration of monomers (T).
ÉÍ-DVE-- FN)— _ k (DVE*)(FN)-(DVE*-> FN)(k' + k' .(T)) = 0
at dr d rl
k' I , 4,e,(DVE)
R. = k1 d(DVE* —» FN) k,df^td 'd(T)-
d rl

79
Dependence of Feed Composition on Rates
It was of considerable interest to measure the rate of copolymeriza¬
tion obtained for different feed compositions. As explained later, the
study of the rate as a function of the feed composition when the total
monomer concentration is kept constant should give information on the
role of the charge transfer complex in the mechanism of copolymeriza¬
tion.
The effect of the variation of the concentration of the reactants
on the rate of a photochemical reaction is difficult to determine
unless the rates are corrected to a constant absorbed light intensity
from known variation of rate with the absorbed light intensity.
The rate of copolymerization was measured in acetonitrile. The
samples were prepared as indicated in the experimental section. The
solutions were irradiated at room temperature for a measured period
of time and the reaction was stopped by immediately opening and roto-
vapping to dryness. Methanol was added, and the insoluble polymer was
filtered and washed with methanol, and dried in an oven at 50°C at least
for 4 hours. The actinometer solution was irradiated in the same tube
right after the reaction. The rate was obtained by measuring the
weight of the polymer after drying. The dependence of the light
intensity on rate is reported in Table XII. The linear relation is
shown in Table XIII.
Rates of products formed in secondary reactions (including the
polymerization) usually show some other than first order dependence
on intensity. In general, bimolecular termination by a reaction
involving active chain carrying species results in rates proportional
to the square-root of intensity. Termination which occurs from a first

80
order reaction leads to a rate which is dependent on the first power
of intensity. It was observed that the rates were dependent on an
order between 0.72 - 1 of intensity. It was close to first order for
the equal molar solution at 300 nm. Possibly both the bimolecular and
unimolecular termination are operating in photocopolymerization. The
first order termination is more possible because the propagating radical
may be terminated by chain transfering to solvent and the polar monomers
The dependence of feed composition on corrected rate was listed in
Table XV and XVI and Fig. 15 and 16.
16
The rates were compared at I = 1.52 x 10 photons/sec and
14
6.4 x 10 photons/sec for irradiation at 300 nm and 236 nm respectively
It was observed that at 300 nm, the maximum rate was at f, = 0.5
d
(equal molar solution), but at f^ > 0.5 at 236 nm for both total
concentration [(T) = 2.40 m/1 and 0.60 m/1]. The composition of copoly¬
mers were in the same range (m^ = 0.35-0.48), and not much different
from each other for both wavelengths. Interestingly, at 236 nm, the
rate maximum fell on f = 0.66 and 0.80 for higher total concentration,
(T) = 2.00 m/1, but on f, = 0.55-0.80 for lower total concentration,
d
(T) = 0.60 m/1. The ir and nmr spectra were almost identical. These
facts indicated that the same propagation process was employed. The
different positions of rate maxima were then due to the different
initiation porcesses.
Mechanisms
The kinetical derivation of the overall rate of copolymerization
can be done by assuming the simplest propagation as follows.

81

82
Table XV
The Rate of Copolymerization of DVE-FN System in Acetonitrile
1 ft
at 300 nm, at I - 1.52 x 10 Photons/Sec.
Total
Concentration
(m/1)
fd
Rate3
(mg/min)
Total
Concentration
(m/1)
fd
Rate3
(mg/min)
0.60
1.00
nil
1.20
0.80
0.179
0.60
0.90
0.051
1.20
0.60
0.313
0.60
0.82
0.117
1.20
0.50
0.376
0.60
0.80
0.098
1.20
0.60
0.70
0.131
2.40
0.98
0.087
0.60
0.67
0.154
2.40
0.70
0.475
0.60
0.60
0.150°
2.40
0.60
0.604
0.60
0.55
0.154
2.40
0.50
0.749
0.60
0.52
0.185
2.40
0.33
0.580
0.60
0.50
0.198
2.40
0.60
0.45
0.161 •
2.40
0.60
0.40
0.190
2.40
0.60
0.40b
0.053
2.40
0.60
0.30
0.167
2.40
0.60
0.20
0.147
2.40
0.60
0.00
---
2.40
aThe rates were corrected to I = 1.52 x 10 photons/sec with equation
log rate /rate = log 1.52/1 x 10
k cal exp b exp
Sample was open to air.
c
Average values.

Rate of copolymerization (mg/min)

84
Table XVI
The Rate of Copolymerization of DVE-FN System in Acetonitrile
14
at 236 ran, at I - 6.4 x 10 Photons/Sec.
Total
Concentration
(m/1)
fd
Rate3
(mg/min)
Total
Concentration
(m/1)
fd
Rate3
(mg/min)
0.60
1.00
nil
2.00
0.90
0.0413
0.60
0.90
0.0217°
2.00
0.80
0.0692
0.60
0.80
0.0274C
2.00
0.80b
0.0267
0.60
0.70
0.0231°
2.00
0.66
0.0686
0.60
0.60
0.0229°
2.00
0.50
0.0644
0.60
0.55
0.0303
2.00
0.40
0.0448
0.60
0.50
0.0246°
2.00
0.60
0.48
0.0235
2.00
0.60
0.45
0.0170°
2.00
0.60
0.41
0.0197
2.00
0.60
0.40
0.0179
2.00
0.60
0.31
0.0209
2.00
0.60
0.00
—
2.00
aThe rates were
loe rate ,/rat
, cal
b„
Sample was open
corrected
e = 0.
exp
to air.
to I- = 6.4
72 log 6.4/1
14
x 10 photons/sec
x 10-1 .
exp
with
the equation
°Average value.

Rate of copolymerization (mg/min)
Fig. 16 The dependence of feed composition on rate at 236 nm (I = 6.
x 10l^photons/sec) for total concentration (a) 2.0 m/1, (b) 0.6 m/1.

86
In this copolymerization, the cyclized DVE radical (XXXI)
attacked complex and monomers to produce polymers with 1:1 and 1:2
compositions, respectively. The 1:1 composition cannot be explained
by the polarity of the radical and complex, because the negatively
polarized radical (XXXI) would attack the positively polarized carbon
carbon double bond of an acceptor monomer since polymerization of DVE
under the same condition is negligible. The propagation of the copoly¬
merization can be interpreted as a competition between the acceptor
monomer FN and the CTC toward the cyclized DVE radical (XXXI).
Although the cyclization of the DVE radical (XXXI) could react
preferably with the acceptor such as MAH because the reaction of a
radical and a monomer of opposite polarities would stabilize the
8 0
transition state, the FN may not be so preferable because of the
less polarization then MAH. Thus, the reactivities of FN and the complex
are compatible. As a result, a competition between FN and CTC control
the structure of the copolymer of DVE-FN system. On the other hand,
the complexation of the HOMO of DVE and LUMO of FN would increase the
71
energy of HOMO of DVE and make the CTC more reactive toward the
destabilized cyclized radical (XXXI) than the uncomplexed DVE.
In equations 22 and 23,' the cyclization may proceed by both
concerted and stepwise processes. A fast cyclization has been observed
for this cyclocopolymerization, which indicated a concerted mechanism.
But some results showed the stepwise mechanism, especially for the
fact that both cis and trans disubstituted ring units were obtained in
the analysis of spectra. A stepwise cyclization cannot be ruled out.
However, by assuming a fast stepwise cyclization (probably just a little
slower than the cis-trans rotation around the disubstituted single bond)

87
of radical XXXII, the same result will be concluded as with the
concerted process as far as rate is concerned.
CN
XXXII
By assuming only the cross-termination
m1‘ + m /
tl2
-» dead polymer
and the steady state:
kl2(TTli* )(M2) = k01(m9*)(M1)
VV 2
Ri = Rt = 2ktl2(m1-)(m2-) = 2kn2 Then, by assuming (DVE —> FN) - K (FN)(DVE)
c
R .k
Rate = ( )1/2(DVE)1/2(FN)K 1/2[2kno + k K (DVE)l
9v w c 12 11 c
2R12ktl2
By definition (FN) = (1 - fJ)(T), (DVE) = f (T)
d d
where (T) = total concentration =( FN) + ( DVE), f = (DVE)/(T)
d
The rate maximuni is a function of (T) and will be at f^ = 0.5 by keeping

88
(T) constant, only when
2k
(DVE) =
12
k^K
11 c
This was not the case for copolymerization irradiated at 300 nm
where the maximum rate was at f, = 0.5 for (DVE) = 1.2 m/1 at (T) =
a
2.40 m.l and (DVE) = 0.3 m/1 at (T) = 0.60 m/1.
By assuming the noncoupling termination as suggested by the rela¬
tionship between rate and intensity,
k21Ml
Ri= h = kt(mi * m2> =
t 1)(m*)
Rate = 2k1,_)M9(m^) t
k01K R.
21 c i
(FN)(DVE)
[2k + k K (DVE)]
12 11 c
Ck12 + k2iKi(DVE)]
As discussed before, K =0.10 1/mole, therefore, for a solution with
c
1.2 m/1 of DVE and 1.2 m/1 of FN in acetonitrile,
(DVE —> FN) = K (DVE)(FN) = 0.144 m/1,
c
The concentration of complex existing in the solution is of the order
of 10% of the monomers. The reactivity of the complex must be very
large compared to the monomers in order to compete with the free monomer
addition.
By assuming k21’k11>>ki2
k K (DVE)»2k 9
11c 12
k21Kc(DVE)»k12
Then
k K R.
11 c 1
Rate
(FN)(DVE)

89
If is independent of monomer concentration, rate will reach
maximum at f^ = 0.5 by keeping (T) constant.
This was the case for copolymerization of DVE and FN in aceto¬
nitrile at 300 nm with (T) = 2.40 m/1, 0.60 m/1.
As discussed before, R. is a function of concentration and
i
should be considered in the rate derivation. At 300 nm,
R. = [k,I , $ ]/[kj+k , (T)] 'where I , = I at 300 nm.
i d abs c d rl ' abs c
k K k I
Rate = 11 C. d abS [$ (FN)(DVE)]/[k +k _(T)]
k^ c d rl
When (T) is kept constant, the rate maximum will be at f^ = 0.5.
If f is kept constant instead, by variation of the total concen¬
tration, the rate will be linear to (T).
(DVE) = f,(T), (FN) = (1-f,)(T),f,
d d d
(DVE)
(t)
Rate a
(FN)(DVE)
k tk (T)
d rl
(l-fd)fd(T)-
kd+krl(T).
The deactivation process is usually quite large compared to the
dissociation.
k (T)»k,, R. = k,I . $ /k _(T)
rl did abs c rl
then,
(Eq. 24)
Rate a (T)2/k ,(T) a (T).
rl
This fact was confirmed by Table XVII and Fig. 17, where the rate is
proportional to (T), (slope = 1.0) at f^ =
0.6 and 0.5.

90
Table XVII
The Dependence of Total Concentration on Rate
Wavelength
fd
(T) m/1
Ratea(mg/min)
Slopeb
cb
300 nm
0.50
0.60
0.198
0.96
0.998
300 nm
0.50
1.20
0.376
300 nm
0.50
2.40
0.749
300 nm
0.60
0.60
0.150C
1.00
0.994
300 nm
0.60
1.20
0.313
300 nm
0.60
2.4
0.604
236 nm
0.60
0.60
0.0246d
0.77
0.839
236 nm
0.60
1.20
0.0300e’ d
236 nm
0.60
2.00
d
0.0644
236 nm
0.80
0.60
0.0274d
0.77
1.00
236 nm
0.80
2.00
0.0692d
3 16
Rates were corrected to I = 1.52 x 10 photons/sec.
bThe slope of the equation: log rate â– = a + b log (T)
C is the correlation coefficient.
°Average value.
d 14
Rates were corrected to I = 6.4 x 10 photons/sec.
6 ...
Calculated from equation m Table XV.

Log rate x 10 mg/min
91
Log (T) x 10 m/1
Fig. 17 The dependence of total concentration on rate
(x) at 300 nm, f = 0.5, (i) at 300 nm, f, = 0.6
(o) at 236 nrfi, = 0.5, (•) at 236 nm, f^ = 0.8

At 236 nm,
92
R.
i
k'l , $,e,(DVE)
d abs d d
k'+k' (T)
d rl
k'l , $,e,(DVE)
d abs d d
k' (T)
rl
where
(k' (T)>>k )
rl d
k 'k K I
Rate = d 1.1 C--a~S [‘J>,e,(DVE)2(FN)]/[k’ (T)]
k^ d d rl
When (T) is kept constant,
Rate a (DVE)2(FN)
Rate will be maximum at (FN)/(DVE) -1/2
i.e. f = 2/3, the rate maximum is at DVE rich region.
This is similar to the case observed for copolymerization of DVE
and FN with (T) = 2.00 m/1 where the rate maximum was in the DVE rich
region, f >2/3, probably due to the fact that both the excited
Q, ma x
DVE and the exciplex (DVE* —> FN) are more or less preferred to be
deactivated by FN through polar coupling.
ground state molecules
When f is kept constant,
Rate a (DVE)2(FN)/k'n(T) a f2(l-f,)(T)3
rl d d
This is not consistent with the experimental results. The exciplex
(DVE* —» FN) can transfer into a lower energy state which is the excited
complex (DVE —> FN)*. All the excited states DVE*, (DVE*—> FN) and
(DVE —> FN)* are possibly deactivated by coupling with polar species

93
(monomers and complex)(Scheme IV).
DVE ;3^ -nrn- > (DVE)* (-fN) > (DVE* -> FN) > (DVE -> FN)* 2R*
I í>
d d
"DF
coupling
coupline
deactivation
deactivation
1 1
V
coupling
deactivation
Ground State Molecules
Scheme IV
Taking this into consideration, the deactivation of excited states can
be assumed to be proportional to k^(T)n(FN)m by the fact that both
monomers and complex may deactivate all the excited complexes and FN
is preferred to some extent.
Then,
R.
i
k I í> £ (DVE)
d abs c c
k" (T)n(FN)m
rl
(dve)2(fn)1 m
k" (T)n
(Eq. 25)
The rate maximum will be at
(FN)/(DVE) = , i.e., fd = 2/(3-m)
The contribution of FN to deactivation is partly included in (T)n term,
it is reasonable to assume that 0 d
Although the exact position of the maximum rate at 236 nm was not
known, a maximum at f = 0.66-0.80 was observed which was predicted by
the proposed deactivation mechanism. When f is kept constant:
Rate a [f2(l-f,)1"m(T)3"m]/[k1' (T)n] a (T)3-m"n = (T)X where x=3-m-n.
a d rl

94
There are three excited states involved. It can be assumed that
3>n>2.
Rate a (T)‘, where x = 3-m-n This is the case observed for copolymerization at 236 nm where
Ratea(T)°'77(Table XVII and Fig. 17).
14
In Table XIV the rate ratio at I = 8.86 x 10 photons/sec at
236 nm to the rate at 300 nm was the same as the quantum yield ratio.
Apparently, the difference of the rate and quantum yield between 236 nm
and 300 nm was based on the same factor, probably the initiation rate,
because only the primary radical formation was a function of wavelength.
By definition, quantum yield ($) is the number of copolymer molecules
formed per photon absorbed.
$ = No. of copolymer molecules formed/no. of photons absorbed.
= No. of primary radicals formed per sec/no. of photons absorbed
per sec.
= R./I .
i abs
Therefore, from Eq. 24 and 25, when (DVE) = 0.71, (FN) = 0.47, (T) = 1.18.
<í> R
300 _ Í300
í> R
236 i236
$ k" (T)n(FN)m
c rl
$,£ (DVE)k _(T)
d d • rl
(DVE)_1(FN)rn(T)n
Vdkrl
1
By assuming that 3>n>2, m = 1, the two deactivation constants are similar
in the order of magnitudes, k" /k' - 1, and e, is in the order of
rl rl d
2 3 1
10-10 . Therefore, (DVE) (FN)m(T)n - 0.78-0.92 Then
$
300
$
236
< $ /(í> £,)<( 1/102 x $ /$,)<1
c d d c d
where $ /$, is
c d
less than 10 .

95
Although the exact value of the parameters were not obtained, it
is reasonable to say that $ is larger than $ and the same result k
Zob oUU
applies for the rates where rate OUU ¿OU
light intensity absorbed. *
In conclusion, the proposed propagation process is consistent with
the experimental results provided that the excited states are deactivated
by collision with the monomers or complex and the proposed initiation
process for photocopolymerization initiated by the charge-transfer
complex mechanism. These postulations are also supported by the fact
that the rate maximum at 236 nm for lower total concentration (0.6 m/1)
was at the position between f = 0.55-0.80 and is less than that for
higher total concentration (f^ = 0.67-0.80) for (T) = 2.00 m/1).
At 236 nm,
R.
k I , $ e (DVE)
d abs d d
k" (T)n(FN)m
rl
due to the preference of FN in the deactivation processes, for lower
concentration, this preference is lost and
R.
i
k I $ e.(DVE)
d abs d d
• k" (T)n
rl
which leads to the maximum rate near f. = 0.67. At 300 nm, the rate
d
maximum is not dependent on the total concentration, indicating that
there is no preference deactivation by FN. This can be understood on
the basis that the electron distribution or energy distribution is
more symmetric in excited complex (DVE —> FN)* than in the exciplex
(DVE* —> FN). In the exciplex, partial excitation is localized on DVE
part and deactivation is preferred by the opposite polar molecule such

96
as FN. Even more, the excited state of DVE is more preferable to
de-activated by FN.
With the proposed mechanism, it is possible to calculate the
reactivity ratio of k /k , i.e. the ratio of the reactivities of the
complex and the acceptor toward the cyclized radical XXXI.
Considering the following reaction scheme:
m^ +
m^ t M2
m* t M
11
'12
21
m:
mi
where is the complex, M0 is the acceptor, m* is the cyclized radical,
and m* is the acceptor radical, and by assuming a steady state, a
copolymer composition equation can be obtained with m^ as the mole
fraction of DVE in the copolymer, (M ) and (M^) as the concentrations
of and MQ, respectively.
mi -dCM^/dt + ^2^2^
n^“ = -d(M2)/dt " k12(M2) = 1 + r! (M2)
where r^ is the reactivity ratio (k^/k ).
equation,
3m,-l
d
l-2m
d
r K f,(T)
led
After rearranging the above
By plotting the left hand side against f^, the reactivity can be ob¬
tained from the slope, the equilibrium constant, and the total
concentration (t). In Table XVIII the calculated reactivity ratios are
shown.
As shown in Fig. 18, the correlation coefficients are small.
However, the estimated value for r K (T) can be obtained as in Table XVIII.
1 c

97
Table XVIII
The Determination of Reactivity Ratio r^
At 300 nm
At
236 nm
With AIBN3
f
3m -1
d
md
i—1
1
T)
£
CO
-f
md
3m -1
d
bd
md l-2m
d
l-2mJ
d
bd
l-2m,
d
0.2
0.35 0.178
0.436
0.08
0.374
0.48
0.2
0.383
0.64
0.4
0.412 1.34
0.400
1.00
0.4
0.383
0.64
2.41
0.5
0.393
0.64
o
CT)
0.372 0.453
0.436
1.22
0.75
0.396
0.90
0.85
0.41
1.28
CO
O
0.410 1.28
0.408
0. 95
0.45
3.50
r K (T)
1 c
1.50
2
. 75
2.24
rl
8b
rO
CO
1—1
16C
aRef. 32,
the reaction was
carried
out in DMR
with
(T) = 1.1-4.
5 m/1.
b(T) = 2.0 m/1, K = 0.10.
c
c
An average value of (T) is assumed as 2.8 m/1, the K is assumed
as 0.05.

-2m
98
Fig. 18 The determination of reactivity ratios
(T) = 2.0 m/1, at 300 nm
(T) = 2.0 m/1, at 236 nm
(T) = 1.1-4.5 m/1, with AIBN

99
A value approximately in the order of 10 was obtained, which is con¬
sistent with the assumption that the reactivity of the complex towards
the cyclized radical is high and the relation
In summary of this chapter, a reaction mechanism including the
participation of complex in both initiation and propagation was
proposed and all the experimental results have been explained.

CHAPTER IV
EXPERIMENTAL
Materials
Fumaronitrile (from Aldrich), m.p. 94-5°C, and maleic anhydride
(from Fisher), m.p. 56-7°C, were recrystallized from benzene and either
sublimed before use or stored in a refrigerator. Divinyl ether (DVE)
was prepared by dehydrohalogenation of bis(2-chloroethyl)ether
(from Eastman) with KOH in triethanol amine at 170-90°C and redistilled
81
before use. Reagent chemicals were used for actinometry. Reagent
grade azobisisobutyronitrile (from J.T. Baker) was recrystallized from
reagent grade methanol, filtered and dried in vacuo in the presence
of Po0(.. The purified AIBN was kept in the refrigerator. For some
syntheses and kinetic runs reagent grade solvents were purified by
the following methods and distilled before use or stored in a
desiccator in order to keep the solvent as dry as possible.
Benzene: Analytical grade benzene (from Mallinckrodt) was stirred
with concentrated sulfuric acid for two days. It was then washed with
dilute, aqueous KOH (5%) solution three times, followed by washing with
water three times. The washed benzene was dried over Linde 3A Molecular
Sieve and distilled over phosphorus pentaoxide in a nitrogen atmosphere,
and stored in a colored bottle in the desiccator.
Acetone: Analytical grade acetone (from Mallinckrodt) was dried over
Linde 3A Molecular Sieves and distilled from phosphorus pentaoxide or
calcium hydride.
100

101
Acetonitrile: Analytical grade acetonitrile (from Mallinckrodt)
was distilled from phosphorus pentaoxide. It was then refluxed over
calcium hydride (5 g/liter) for at least an hour, then distilled
slowly, discarding the first 4 and the last 10% of the distillate.
Xylene: Analytical grade xylene (from Mallinckrodt) was distilled
over calcium hydride and only the middle cut was collected.
Chloroform: Analytical grade chloroform (from Mallinckrodt) was
shaken with concentrated sulfuric acid, washed with water, dried over
calcium chloride and distilled over calcium hydride.
Diethyl ether (from Mallincdrodt) was distilled over calcium
hydride.
Tetrahydrofuran: Analytical grade tetrahydrofuran (from Mallinckrodt)
was refluxed and distilled over lithium aluminum hydride just before use.
Equipment and Data
For photolytic reactions, the glassware was cleaned with acidic di¬
chromate solution, then washed and dried in an oven overnight.
Melting point determinations below 250°C were carried out in open
capillary tubes in a Thomas-Hoover Melting Point Apparatus. The melt¬
ing point determinations over 250°C were carried out on a Fisher-Jones
Melting Point Apparatus.
All temperatures reported were in degrees centigrade and were
uncorrected. Pressures were expressed in millimeters of mercury,
having been determined by means of either a Zimmerli or McLead Gauge.
Infrared spectra were obtained with a Beckman IR-8 or IR-10 Double¬
beam Infrared Spectrophotometer. Ultraviolet spectra were run on a
Beckman-DK-2A Double-beam Recording Spectrophotometer.
60 MHz Nuclear Magnetic Resonance (nmr) spectra were obtained on a
13
Varían Associates Analytical NMR Spectrometer, Model A-60. C Nmr

102
spectra were recorded on a Varían XL-100 pulse-FT spectrometer at
25.16 MHz, using broad-band decoupling at 100 MHz.
Intrinsic viscosities were calculated from efflux times of
solutions through a Cannon-Ubbelohde Semi-micro Dilution Viscometer
placed in a 30°C to 1°C constant temperature water bath.
Copolymer composition was calculated from carbon and/or nitrogen
analysis by Heterocyclic Chemical Corp., Galbraith Laboratory, Inc.,
or PCR Microanalytical Laboratories. The copolymers of DVE-MAH and
DVE-FN were found almost invariably to be associated with water.
The copolymer samples sent for analysis were purified at least twice
by precipitation followed by drying in vacuo at 56°C or 50°C for more
than 3 days.
Irradiation Source
For synthetic experiments above 300 nm, a Hanovia High Pressure
Mercury lamp (450 Watts, cat. no. 679 A-36) equipped with quartz
water cooling system was employed as the light source.
For monochromatic light irradiation, the source was a 2500 Watt
Mercury Xenon lamp (Hanovia type 929B-9U) contained in the Schoeffel
LN 152N/2 Lamp Housing (supplied with 21/4" diameter variable focus
double quartz condenser, parabolic reflector, cooling fan, and finned
heat sinks for the arc lamp). The output beam is deflected through a
Schoeffel LHA 165/2 Stray Light Reducing and Illumination Predispersion
Prism, assembly into a Schoeffel GM 250 High Intensity Monochromator
(focal length 0.25 m, linear dispersion 3.2 nm/mm, grating blazed at
300 nm with 1180 grooves/mm, aperture ratio f/3.9). The power supply
for the lamp is a Schoeffel CPS 400 equipped with the Schoeffel LPS
400S starter with operates the lamp at 50 V and 50 A.

103
UV Studies
The spectrometric studies of complexations were carried out with
a Beckman DK-2A Spectrophotometer with quartz cells with 1 cm path-
length. For studying pure DVE and FN, pure acetonitrile was used as
reference. For the studies of the complex, the reference cell was
filled with FN in acetonitrile at the same concentration as in the
complex solution cell. The absorbance of pure DVE at the same concen¬
tration was deducted from the absorbance measured because FN and DVE
present some residual absorption below 300 nm. The exact value of the
absorbance of the complex could be evaluated. The conditions of
measurements are shown in the respective tables and figures in the text.
Syntheses Related to Monomer Preparation
Divinyl Ether
This compound was prepared following the procedure of Shastakuvskii
81
and Dubrova. A 3 liter, three-necked flask was equipped with a
mechanical stirrer, an addition funnel, a reflux condenser and a
thermometer. Into this flask was placed 1000 g (17.8 mole) of analy¬
tical grade potassium hydroxide and 200 g (1.41 mole) of triethanol
amine. With the object of removing divinyl ether from the sphere of
reaction as fast as it was formed, warm water (35°C) was passed through
the reflux condenser, which was connected to a condenser with ice water
cooling. A two necked round bottom flask as receiver was connected
to this distillation condenser and immersed in an ice water bath. The
second neck of the receiver was connected with a drying tube. The
mixture of potassium hydroxide and triethanol amine was preheated
until K0H was melted (about 190-210°C). With stirring, 400 g (2.79 mole)
of bis(2-chloroethyl ether, b.p. 91°C/37mm) was added slowly from the

104
addition dropping funnel to the alkaline solution with the mixture
temperature between 160 and 190°C. A white fume, which was tested as
basic, was observed right after the addition. Liquid DVE was collected
two hours after all starting material was added. Further refluxing did
not improve the yield significantly. The product was washed three
times with precooled water to prevent evaporation of DVE. Then, after
washing three times with cold hydrochloric acid (5%), followed by
washing three times with cold deionized water, the resulting organic
layer was dried over calcium chloride overnight. After refluxing and
distilling over calcium hydride, the product was kept in the refrigera¬
tor. The purified product was 75 g (27% yield) of pure divinyl ether,
b.p. 29-29.5°C. The literature gave b.p. 28-29°C. The ir spectrum was
identical to the reported spectrum. Nuclear magnetic resonance spectrum
(Fig. 19a) showed a clear ABX pattern in the olefinic hydrogen region.
Little or no impurities were detectable in the nmr spectrum.
Bis(2,2-didetueriovinyl)ether
2,2,2',21 -Tetradeuteriodiethylene glycol.^ A 300 ml three necked
round bottom flask was equipped with a reflux condenser, an addition
funnel, a mechanical stirrer, and an inlet for maintaining a slightly
positive dry oxygen-free nitrogen pressure. To 200 ml of THF which was
freshly distilled from lithium aluminum hydride, was added 8 g of
lithium aluminum deuteride (0.19 mole). The mixture vías stirred under
reflux for 30 minutes. Sublimed diglycolic anhydride (18.4 g, 0.16 mole)
(from Aldrich), m.p. 92-93°C, dissolved in 150 ml of freshly distilled
THF, was added with stirring at a rate maintaining gentle reflux. The
mixture was stirred with refluxing under nitrogen overnight. After
cooling, the reaction mixture was hydrolyzed with 30 ml of deionized

Fig. 19 60 MHz nuclear magnetic resonance spectra of (a) DVE, (b) DDVE with 250
ppm sweep width, (c) DDVE with 100 ppm sweep width.
105

106
water in ice bath. After the ice bath was removed, the mixture was
stirred for 10-20 minutes. The precipitate was filtered out and stirred
with 30 ml of 0.6 N sulfuric acid and 100 ml of THF. The mixture was
filtered. After extracting the solid three times with 100 ml of THF,
the resulting extracts were combined with the previous filtrates and
dried with excess anhydrous potassium carbonate overnight with stirring.
THF was rotavapped and a slightly yellow oily compound with some solid
suspension was left. This compound was carefully filtered and distilled
under vacuum. A colorless compound was collected at b.p. 102-105°C/lmm,
yield 8.6 g (49%). The ir spectrum of this product was similar to
diethylene glycol but with new absorption bands at 2220 and 2110 cm \
The ir spectrum (neat) of the compound showed absorption bands at
2840-2980 (s,b), 3040-3520 (s,b), 2220 (m), 2110 (m), 1740 (m, multiple),
1650 (m, multiple), 1350 (m with shoulder around 1450), 1260 (m),
1170 (s), 1110 (s,b), 1030 (m), 970 (m), 850 (m,b), 800-600 (s, broad
with shoulder at 800 cm ^).
The nmr spectrum (Fig. 20a) (CDC1 ) of the compound showed a singlet
peak at 6 4.45 and 3.58 ppm, with an area ratio 1:2. In contrast, a
multiple absorption centered at 5 3.65 ppm was observed in diethylene
glycol with a ratio of 4:1 ‘to the singlet at 8 4.94 ppm.
The same procedure was applied to prepare diethylene glycol from
diglycolic anhydride and lithium aluminum hydride. The resulting
product (b.p. 97-101°C/l mm, reported 110°C/3 mm) showed exactly the
same ir and nmr spectra as the literature.
51
Bis(2-bromo-2,2-dideuterioethyl)ether. Phophorus tribromide (23.8 g,
0.09 mole) was placed in a flask equipped with a mechanical stirrer,
dropping funnel, and a reflux condenser with a calcium chloride tube.

HOCD-
H I I 1? I 1 ¡ i
5.0 H.O 3.0 5.0 3-0 2.0 1.0
ppm (6)
Fig. 20 60 MHz nuclear magnetic resonance spectra of (a)
2,2,2’,2'-tetradeuterodiethylene glycol, (b) diethylene
glycol.
107

108
A solution of 11.7 g (0.11 mole) of bis(2,2-dideuterioethyl)ether in
3.3 g (0.04 mole) of freshly distilled pyridine was slowly added with
dry ice-acetone cooling. The mixture was left overnight and warmed
up to room temperature. The liquid portion was extracted with ether,
washed with 0.1 N hydrochloric acid and water and dried with anhydrous
sodium sulfate. After filtration, the filtrate was distilled under
vacuum after rotavapping the ether. The product was collected at
75-77°C/3.5 mm. Yield: 19.1 g, 76%.
The ir spectrum of the product was similar to the nondeuterated
bis(2-bromoethyl )ether, but with a new absorption band at 2170 cm ^.
The ir spectrum (neat) of the compound showed the absorption bands
at 2850-2950 cm ^ (m,b), 2171 cm ^ (weak), 1470 (m, multiple), 1360 (m),
1285 (m), 1260 (m), 1140 (m), 1105 (s, multiple), 1000 (m), 930 (m),
180 (w) cm "*â– .
The nmr spectrum (neat) of the compound showed only a clear sharp
singlet at 5 3.80 ppm with half width 3 ppm (Fig 21a).
This same procedure was applied to prepare bis(2-bromoethyl)ether
from diethylene glycol. The resulting products (b.p. 92-3°C/12mm, lit.
8 2
115°C/32 mm) showed exactly the same ir and nmr spectra as in the
literature with a clear AArBB'.nmr absorption pattern. (Fig. 2lb).
Bis(2,2-dideuteriovinyl)ether. Similar to the preparation of divinyl
81
ether from dichloro starting material, 21.7 g (0.39 mole) of potassium
hydroxide and 11.8 g (0.083 mole) of triethanol amine was added into a
50 ml three necked round bottom flask equipped with a mechanical stirrer,
an addition dropping funnel, thermometer and a 35°C reflux condenser
which was then connected to a distillation condenser leading to two
necked receiver with drying tube. Purified bis(2-bromo-2,2-dideuterio-

109
/°\
BrCD —CH2 CH2
BrCD,
/°\
BrCH—CH2 CH2
BrCH.
, . | — [
4.0 4.0 3-0
ppm ( Fig. 21 60 MHz nuclear magnetic resonance spectra of (a)
bis(2-bromo-2,2-dideuteroethyl)ether, (b) bis(2-bromoethyl)
ether.

110
ethyl)ether (18.3 g, 0.078 mole) was added to the melting mixture at
190°C. The product was washed with deionized water and distilled over
calcium hydride. Yield: 1.5 g (26%) purified product, B.p. 30-31°C.
The nmr spectrum (neat) (Fig 19b) of the compound showed a multi-
plet centered at 6 6.4 ppm instead of the ABX pattern of divinyl
ether. Only a little impurieties were observed on the nmr spectrum.
The multiplet was further examined with 100 cps sweep width; a clear
splitting pattern was observed with a ratio of approximately 1:1:2:1:2:1:1
corresponding to a H-D cis coupling and H-D trans coupling with 'Jp¡¡-)cps=1
Hz and JttT, = 2Hz, respectively.
HD, trans ’ ^ J
This same procedure was applied to prepare divinyl ether from
bis(2-bromoether)ether. Divinyl ether was obtained as confirmed' by
the ABX pattern on nmr spectrum.
Copolymerization
Photocopolymerization of DVE-FN System
General photocopolymerization procedure. DVE and FN were weighed
and dissolved in the solvent in volumetric flasks. The solutions were
transferred to Pyrex or Quartz tubes. The contents of the tubes were
frozen with liquid nitrogen and the tubes were evacuated on a vacuum
line. The freeze-pump-thaW cycle was repeated at least three times
-5
under pressure of 10 mm Hg or better and the tubes were then sealed.
The quartz tubes (21 mm o.d.) were joined to a Pyrex section by graded
seal. The tubes were irradiated for a period of time, while being
rotated on their axis by a rotavapor motor (Buchi Corp.) or an electric
motor. A lens supplied by Schoeffel Co. transforms the exit beam of
the monochromator into a thin line such that only the center portion of
the tube is irradiated. The polymerization rate of the polymer was

Ill
measured by precipitation and weighing after evaporation.of the
irradiated solution and drying in a vacuum oven for at least 4 hours
at 50°C. The results were shown earlier.
Copolymerization with additives. Some additives has been added into
DVE-FN system. The results are listed in Table XIX.
Table XIX
The Copolymerization of DVE-FN System with Additives
Additives
Concentration
m/1
Wavelength
nm
Yield/min.
mg/min
No additive
236
0.036
300
0.36
NEt3
0.1
236
0
300
0
0.01
236
0
300
nil
DPPH
0.009
236
0
300
0
-5
3.5 x 10
236
0.035
300
0.129
Chloranil
.0.006
363
0
Note: 1. [DVE]
=[FN]= 0.6 m/1.
2. DPPH
is diphenyl picryl
hydrazyl radical.
The light intensity and the quantum yield measurement. The intensity
of the light absorbed by the comonomer solution during photocopolymeriza¬
tion was measured in the same reaction tube. After the irradiation of
sample, the tube was emptied and filled in the dark with known amounts

112
of the actinometer solution by pipettes. In the tube which holds 15 ml
i
solution, the following procedure was used.
To the tube which may be wet after having been washed with water
in the dark was pipetted 15.0 ml of the actinometer solution and
irradiated for an exact period of time according to the wavelengths.
After irradiation, the contents were poured into a 50 ml volumetric
flask through a funnel to avoid spillage and rinsed twice with about
5 ml portions of distilled water. To the irradiated actinometer
solution and a dark standard was added 2 ml of the 0.1% phenanthroline
aqueous solution and 10 ml of the NaOAc-H9SO^ buffer solution, and
diluted to the mark with distilled water. The solutions were left at
least one hour or overnight in the dark. The Beckman DK-2A ultraviolet
spectrophotometer was zeroed at 510 nm using the dark standard sample
in the sample and reference beams. Each irradiated actinometer solution
was analyzed at 510 nm on the absorption scale.
To calculate the light intensity:
20
photons/min = 6.02 x 10 VA/le x 1/Tt
A = Volume of the actinometer solution whose absorption was
measured = 50.0 ml.
1 = Path length of the.cell = 1.0 cm.
£ = Extinction coefficient of the actinometer = 11100.
T = 1.24 and 1.25 at wavelengths larger and smaller than 254 nm,
respectively.
t = Time the actinometer was irradiated.
The irradiation time was adjusted so that the absorbance was around
0.6-0.8. The quantum yield of the photocopolymerization could be
obtained.

113
$ = No. of copolymer molecules produced/no. of photons absorbed.
= Wt. of copolymer/average molecular weight of the copolymer
23
6.02 x 10 /It.
ir
I = Light intensity absorbed by the actinometer solution.
t^ = The time polymerization solution was irradiated.
For DVE-FN system, the average molecular weight of the copolymer
vías obtained by Zeegers and Butler as 4600 and 5500 at the total
39
concentration of 1.2 m/1 and 1.8 m/1, respectively. For other
concentrations the molecular weight may be slightly different, but
within the same order.
82
The preparation of actinometer solution. The solution was pre¬
pared by dissolving 295 mg of the K^FeiC^O^) crystals, in 80 ml of
distilled water, followed by adding 5 ml of 1 M HoS0^ and diluting to
100 ml mark. All operations were made in the dark with an infrared
light. The buffer solution was prepared by dissolving 81.7 g of NaOAc
in 600 ml of water. The solution was filtered into a 1000 ml volumetric
flask, 180 ml of 1 M ILSO, was added, and diluted to the mark.
The Synthesis of Copolymer of DVE-FN System
For synthetic runs for this system, the reactions were allowed to
proceed more than 40% in order to get large enough amounts of sample for
13
C nmr spectroscopy and other analyses. In general, a 0.6 m/1 of DVE
and 0.6 m/1 of FN solution was prepared in acetonitrile with or without
_3
3.1 x 10 m/1 of AIBN. After three freeze-pump-thaw cycles, the sample
was sealed. For 236 nm, the Schoeffel set up was used to irradiate the
sample in quartz tube for 24 hours; 40% conversion was obtained. For
300 nm, the Hanovia high pressure mercury lamp (450 Watts) was used to
irradiate a sample in a pyrex tube at room temperature, so that light

114
with wavelength shorter than 310 nm was filtered out. After 17 hours
irradiation, 55% conversion was obtained. For free radical initiation,
the sample was heated in an oil bath at, 63°C for 10 hours; 44% yield was
obtained. The resulting polymers were purified at least twice by
dissolving in acetonitrile and precipitating from methanol. They were
dried at 56°C in vacuo overnight. The analyses were shown earlier in
the text.
Copolymerization of DVE-MAH System
General copolymerization procedure. A three necked round bottom
flask was equipped with a mechanical stirrer, a nitrogen inlet and
a rubber septum. The nitrogen inlet was connected to a trap filled with
molecular sieves (4A) leading to a water free nitrogen source with a
concentrated sulfuric acid bubbler. The flask was flushed with nitro¬
gen for one hour with the septum open. With positive nitrogen flow,
an appropriate amount of MAH (usually 1.96 g) was added followed by 35 ml
of dry solvent, and the septum was replaced. In a 25 ml two necked
pear shaped flask, an appropriate amount of AIBN (usually 13.6 mg) was
added under positive nitrogen flow. Both necks were then sealed with
septums. Usually, 1 ml of purified DVE was added through the septum
with a syringe, followed by 5 ml of the dry solvent. The 100 ml reaction
flask was preheated to the desired temperature by means of a constant
temperature oil bath. With stirring, the DVE-AIBN solution was added
through the septum by syringe as quickly as possible. After stirring
for an appropriate time, the reaction was stopped by cooling with an
ice bath and the septum was opened. The contents were filtered with a
sintered glass filter (5 ml, medium porocity) and washed with dry diethyl
ether. The resulting solid was purified at least once by dissolving in

115
dry acetone and precipitating from diethyl ether. It was then dried
at 50 or 56°C in vacuo for 3 days.
In this preparation the concentrations of MAH, DVE, and AIBN were
-3
approximately 0.50, 0.28, and 2.1-2.5x10 m/1, respectively.
For photocopolymerization at wavelengths longer than 300 nm,
a sample was prepared in the same manner as described for DVE-FN
system. The results are listed in Table XX.
It was observed that part of the copolymer prepared in benzene was
not soluble, especially with higher conversion. The resulting soluble
copolymer dissolved only in very polar solvents such as DMSO and DMF.
The DMSO solution of the copolymer from the higher conversion experi¬
ments behaved irregularly on viscosity measurements, (Fig. 22).
It was then necessary to prepare soluble copolymer in solvents with high
chain transfer character. The results are shown in Table XX.
The Copolymerization of MAH with Bis(2,2-dideuterioethenyl)ether in
Cyclohexanone
The same procedure as described for DVE-FN system was applied for
the radical initiated copolymerization of bis(2,2-dideuterioethenyl)ether
with MAH in cyclohexanone. Deuterated DVE (0.2782 g) was reacted with
0.9128 g of MAH in the present of AIBN ^2.4x10 ^ m/1) in cyclohexanone
at 72°C for 2 hours. Yield: 1.01 g (85%). The copolymer was purified
by dissolving in dry acetone and reprecipitating from dry diethyl ether.
It was then dried under 10 u mm Hg at 50°C for 3 days.

Table XX
The Copolymerization of DVE-MAH Syst
Solvent
Temperature
Q
Concentration(m/l) Initiation
DVE FN
Time
min.
Benzene
51-54
0.25
0.50
AIBN
125
Benzene
60-66
100
Benzene
61-64
47
Benzene'
61-62
•
32
Benzene
71-73
•
82
Benzene
76-78
25
Benzene
28-29
>310 nm
600
1140
Xylene
128-132
0.28
0.50
AIBN
15
Xylene
100-104
1.12
0.50
15
C6H10°d
70-72
0.50
0.95
120
CHC13
60-61
0.28
0.50
35
Xylene
29-30
1.12
0.50
>310 nm
990
CHC13
25-26
0.32
0.50
AIBN+>310nm
60
CHC13
>310 nm
240
See next page for footnotes.
at Different Temperatures
Yield
%
Viscosity3
1 Solubility
in DMSO
Composition
C% H% i
25
1.2
Partially
43.83
5.16
85
Insoluble
47
1.4
Partially
44.19
5.14
24
Soluble
86
Insoluble
44.42
4.96
77
1.2
Soluble
10
Soluble
31
0.16b
Soluble
50.49
4.23
62
Soluble
53.75
3.99
51
Soluble
81
Soluble
43
0.22b
Soluble
49.91
4.52 0
44
Insoluble
52.10
4.27
81
Soluble
50.85
3.90
56
Soluble
52.27
3.84
116

Table XX (continued)
aThe reduced viscosity at the concentration between 0.275 g/100 ml and 0.40 g/100 ml in DMSO.
^Intrinsic viscosity in DMSO at 30°C.
c - 3
AIBN concentration is 2.1-2.5 x 10 m/1.
>310 nm: Initiated with 450 Watts Mercury Lamp in a pyrex tube.
AIBN t >310 nm: Initiated with light in the presence of AIBN.
^Cyclohexanone.
117

118
Fig. 22 The viscosities of the DVE-MAH copolymer in DMSO
prepared in (a) benzene at 76-78°C with 77 % conversion, (b)
benzene at 51-54°C with 25 % conversion, (c) benzene at 6l-64°C
with 47 1 conversion, (d) CHCl^ at 60-6l°C with 43 % conversion,
(e) benzene at 28-29°C with 31V» conversion initiated by light.

APPENDIX
STEREOCHEMISTRY BACKGROUND FOR 5,5- AND 5,6-BICYCLIC SYSTEM
IN THE COPOLYMER OF DVE-MAH
Considering the stepwise cyclization involved in the cycloco¬
polymerization described in equation 26, and that the two possible
bicyclic radicals may lead to a cycloco.polymer containing both bi-
cyclic structures:
The following discussion is presented.
In each bicyclic structure, the rings can be fused by either cis
or trans junctions, and in each type of fused ring, system there are
several possible configurational isomers. All the possible configura¬
tional isomers are listed below:
119

120
5,6-Bicyclic Ring System
Trans-fused ring system
5,5-Bicyclic Ring System
Cis-fused ring system

121
By use of models to compare the strain developed in these different
configurations, it is reasonable to compare the models with the substi¬
tuents on equatorial or pseudo equatorial positions based on the small¬
est steric 1,3-interaction expected.
In the 5,6-bicyclic ring system, there are eight possible configura¬
tional isomers for both cis and trans fused ring systems. The trans
isomers are more rigid and more ring strain is expected in these systems.
However, the energy differences between trans and cis isomers may be
small. Although trans-bicyclio(4.3.0)-nonane is more stable (about
1 Kcal/mole) than the cis isomer, the cis hexahydrophthalic anhydride
83
is more stable. It is thus- possible that both trans and cis isomers
may be formed in the cyclocopolymerization.
Consideration of the very large substituents on the 2,6-position
leads to Structures XIa and Xlle as the most plausible configurational
isomers of cis and trans isomers, respectively. In these structures,
the pyran oxygens are anti and syn to the anhydride ring system,
respectively. In all cases the methine hydrogens on the 2,6-positions
are non-equivalent and should experience different chemical shifts in
the nmr spectra. All the other configurational isomers are possible
to some extent. It is assumed that the presence of the other isomers
only broaden the signals of the two methine hydrogens and for the same
reason the two methylene groups are broadened.
The cis isomer for the 5,5-bicyclic system is much favored over
the trans isomer. The heat of combustion of trans bicyclo(3.3.0)
octane is greater than the cis isomer by 6 Kcal/mole.There are four
cis isomers possible. The cis isomers with cis-2,5-substitutions (XlVd)
is most probable with oxygen anti to the anhydride unit. In this isomer,

122
the two methines as well as the two methylene groups are equivalent.
A very small difference is expected between anti and syn cis-di-2,5-
substituted cis-fused bicyclic systems because of the rapid inversion of
the C-O-C linkage relative to the anhydride unit. The isomers with
trans 2,5-disubstitutions are possible but some strain is developed in
order to position the two huge substituents on the pseudo equatorial
64
positions of the half-chair conformation.
In conclusion, quite a few of 5,6-bicyclic isomers are expected
for both cis and trans fused ring systems and the overall consequence
is the non-equivalency between the 2- and 6-methine hydrogens, which
would lead to two broad signals in the nmr spectra. Only cis-fused
5,5-bicyclic ring system is expected and the most probable configura¬
tional isomer could be expected to be a mixed anti and syn cis-2,5-
disubstituted cis-fused 5,5-bicyclic system. This system would lead
to a sharper peak in the nmr spectra. The presence of the possible half-
chair trans 2,5-disubstituted isomers would broaden the signals or even
show up as another signal. No trans-fused 5,5-bicyclic system seems
possible.

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BIOGRAPHICAL SKETCH
Yuan Chieh Chu was born November 16, 1943, at Chian-Du, Chian-Su,
China. In June of 1963, he graduated for the Normal University
Secondary School in Taipei, Taiwan., He received the degree of
Bachelor of Science with a major in chemistry from Chung Yuan Institute
of Science and Engineering, Chun-Li in June, 1969. He attended the
Graduate School of the National Taiwan University where he was awarded
the degree of Master of Science in Organic Chemistry in June, 1971.
He entered the University of Florida in September, 1971 where
he has been working as a teaching and research assistant.
The author was married to the former Rolan Liu on October 24, 197 3 ,
in Gainesville, Florida. He is the father of one lovely child,
Lawrence Chu.
127

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.
"George B. Butler, 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.
Paul Tarrant
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.
0. uiL;
V_.;9 Vv
Willis B. Person
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.
William R. Dolbier, Jr.
â– Professor of Chemistry
V

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.
, -7 .â– 
■'] i ¿ 1.' - ' ^
Thiéo E. Hogen-Esch
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.
Eugen^'P. Goldberg
Professor of Materials Sciences and-A
Engineering and of Chemistry
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Arts and Sciences and to
the Graduate Council, and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
Harry H. Sisler
Dean, Graduate School

UNIVERSITY OF FLORIDA
3 1262 08554 0663





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