Title: Synthesis and polymerization of some non-conjugated dienes
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Title: Synthesis and polymerization of some non-conjugated dienes
Physical Description: x, 103 leaves. : illus. ; 28 cm.
Language: English
Creator: Chu, Shaw-Chang, 1947-
Publication Date: 1974
Copyright Date: 1974
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Subject: Diolefins   ( lcsh )
Polymers and polymerization   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
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non-fiction   ( marcgt )
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Thesis: Thesis--University of Florida.
Bibliography: Bibliography: leaves 99-102.
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Volume ID: VID00001
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SYNTHESIS AND POLYMERIZATION OF SOME
NON-CONJUGATED DIENES












By

Shaw-Chang 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


1974














ACKNOWLEDGEMENTS

The author wishes to express his deep appreciation to

his research director, Professor George B. Butler, whose

guidance, counsel, and encouragement were invaluable during

the execution of this work, and to the members of his super-

visory committee for their advice and suggestions.

The author also wishes to express his appreciation to

his fellow graduate students whose assistance and suggestions

contributed much to this work.

Special thanks are due to Dr. M. Kaufman for correcting the

English of the rough draft and to Ms. A. Kennedy for typing

this dissertation.

Finally the author wishes to express great appreciation

to his wife, Mon-Li, whose devotion, forbearance, and under-

standing during months of neglect made this work possible.

The financial assistance received from the Chemistry

Department and Dr. Butler's research funds is gratefully

acknowledged.















TABLE OF CONTENTS
Page

ACKNOWLEDGEMENTS ii

LIST OF TABLES vi

LIST OF FIGURES vii

ABSTRACT ix

CHAPTER

I. INTRODUCTION 1

General Background 1

Two-Stage Polymerization 2

Chemical Reactions of Polymers 4

Cyclopolymerization of Unsymmetrical Dienes 6

Research Objectives 12

II. RESULTS AND DISCUSSION 16

Synthesis and Polymerization of o-, m-, and p-
(2-Vinyloxyethoxy)styrenes 16

Synthesis of o-, m-, and p-(2-vinyloxy-
ethoxy)styrenes 16

Anionic polymerization of o-, m-, and p-
(2-vinyloxyethoxy)styrene 17

Characterization of the poly-(2-vinyl-
oxyethoxy)styrenes 25

Radical polymerization of o-, m-, and p-
(2-vinyloxyethoxy)styrenes 32

Post-cationic polymerization of o-, m-,
and p-(2-vinyloxyethoxy)styrenes 38


iii









Synthesis and Polymerization of o-, m-, and p-
Vinylphenoxyethanols 40

Polyvinylphenoxyethanols from hydrolysis of
the poly-(2-vinyloxyethoxy)styrenes 40

Synthesis of o-, m-, and p-vinylphenoxy-
ethanols 42

Radical polymerization of o-, m-, and p-
vinylphenoxyethanols 50

Chemical reactions of the polyvinylphen-
oxyethanols 50

Synthesis and Cyclopolymerization of 2-(o-
Vinylphenoxy)ethyl Methacrylate and Acrylate 55

Synthesis of 2-(o-vinylphenoxy)ethyl
methacrylate and acrylate 55

Cyclopolymerization of 2-(o-vinylphenoxy)-
ethyl methacrylate and acrylate 58

III. EXPERIMENTAL 68

Equipment and Data 68

Chemical Source and Purification of Reagents 69

Monomer Synthesis 69

Synthesis of o-, m-, and p-(2-vinyloxy-
ethoxy)styrenes 69

Synthesis of o-, m-, and p-vinylphenoxy-
ethanols 74

Synthesis of 2-(o-vinylphenoxy)ethyl meth-
acrylate and acrylate 76

Polymerization Studies 78

Anionic polymerization of o-, m-, and D-
(2-vinyloxyethoxy)styrenes 78

Radical polymerization of o-, m-, and p-
(2-vinyloxyethoxy)styrenes 84

Post-cationic polymerization of the poly-
(2-vinyloxyethoxy)styrenes 86


__ 1









Polyvinylphenoxyethanols from hydrolysis of
the poly-(2-vinyloxyethoxy)styrenes 88

Radical polymerization of o-, m-, and p-
vinylphenoxyethanols 90

Chemical reactions of the polyvinylphen-
oxyethanols 92

Radical and photo-polymerization of 2-(o-
vinylphenoxy)ethyl methacrylate and acrylate 96

BIBLIOGRAPHY 99

BIOGRAPHICAL SKETCH 103















LIST OF TABLES


Table Page

1. Anionic-Initiated Polymerization of o-,m-,
and p-(2-Vinyloxyethoxy)styrenes 24

2. Tabulation of Maxima in Ultraviolet Spectra 26

3. Radical-Initiated Polymerization of o-, m-,
and p-(2-Vinyloxyethoxy)styrenes 37

4. Cationic-Initiated Crosslinking of Poly-
(2-vinyloxyethoxy)styrenes 39

5. Properties of Polyvinylphenoxyethanols from
Polymer Hydrolysis 43

6. Conditions of Polymerization and Properties
of the Radical-Initiated Polyvinylphenoxy-
ethanols 51

7. Properties of Poly(vinylphenoxyethyl 3,5-
dinitrobenzoates) 53

8. Properties of Polymeric Derivatives from
Poly[2-(o-vinylphenoxy)ethanol] 56

9. Polymerization of 2-(o-Vinylphenoxy)ethyl
Methacrylates and Acrylate 60














LIST OF FIGURES
Figure Page

1. NMR Spectrum of o-(2-Vinyloxyethoxy)styrene 18

2. NMR Spectrum of m-(2-Vinyloxyethoxy)styrene 19

3. NMR Spectrum of p-(2-Vinyloxyethoxy)styrene 20

4. N4MR Spectrum of Poly[p-(2-vinyloxyethoxy)styrene] 21

5. Ultraviolet Spectra of o-(2-Vinyloxyethoxy)-
styrene and the Anionically Initiated Polymer
of that Compound 27

6. Ultraviolet Spectra of m-(2-Vinyloxyethoxy)-
styrene and the Anionically Initiated Polymer
of that Compound 28

7. Ultraviolet Spectra of p-(2-Vinyloxyethoxy)-
styrene and the Anionically Initiated Polymer
of that Compound 29

8. Molecular Weight Distribution Curve of Poly-
[o-(2-vinyloxyethoxy)styrene] 33

9. Molecular Weight Distribution Curve of Poly-
[m-(2-vinyloxyethoxy)styrene] 34

10. Molecular Weight Distribution Curve of Poly-
[p-(2-vinyloxyethoxy)styrene] 35

11. NMR Spectrum of Poly[2-(o-vinylphenoxy)ethanol] 46

12. NIR Spectrum of 2-(o-Vinylphenoxy)ethanol 47

13. NMR Spectrum of 2-(m-Vinylphenoxy)ethanol 48

14. NMR Spectrum of 2-(p-Vinylphenoxy)ethanol 49

15. NMR Spectrum of 2-(o-Vinylphenoxy)ethyl
Methacrylate 61

16. NMR Spectrum of Poly[2-(o-vinylphenoxy)ethyl
methacrylate] 62


vii









17. NMR Spectrum of 2-(o-Vinylphenoxy)ethyl Acrylate 63

18. NMR Spectrum of Poly[2-(o-vinylphenoxy)ethyl
acrylate] 64

19. Infrared Spectra of (A) 2-(o-Vinylphenoxy)ethyl
Methacrylate (VPEM), (B) Radical-Initiated Polymer
of VPEM, and (C) Photo-Initiated Polymer of VPEM 65

20. Infrared Spectra of (A) 2-(o-Vinylphenoxy)ethyl
Acrylate (VPEA), (B) Radical-Initiated Polymer
of VPEA, and (C) Photo-Initiated Polymer of VPEA 66


vii i















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



Synthesis and Polymerization of Some
Non-Conjugated Dienes

By

Shaw-Chang Chu

December 1974

Chairman: George B. Butler
Major Department: Chemistry

Three isomeric non-conjugated dienes, o-, m-, and p-

(2-vinyloxyethoxy)styrenes, were selectively polymerized by

anionic or radical initiators through the styryl double

bond while leaving the vinyl ether moiety intact. The

anionic-initiated polymeric products were of high molecular

weight and narrow molecular weight distribution as charac-

terized by membrane osmometry and gel permeation chromato-

graphy, respectively. These polymers could be subsequently

crosslinked by cationic initiator via the vinyl ether moiety

on the polymer side-chains.

Acid-catalyzed hydrolysis of poly-(2-vinyloxyethoxy)-

styrenes yielded their respective hydroxy-containing polymers,

polyvinylphenoxyethanols. The latter were physically and

spectroscopically identical to authentic samples prepared by









radical polymerization of vinylphenoxyethanols, which, in

turn, were synthesized by hydrolysis of (2-vinyloxyethoxy)-

styrenes. The polyvinylphenoxyethanols could undergo many

chemical transformations, such as esterification with 3,5-

dinitrobenzoyl chloride, cyanoethylation with acrylonitrile

in the presence of a base catalyst, and urethane formation

with isocyanates.

Upon reaction of 2-(o-vinylphenoxy)ethanol with metha-

crylyl and acrylyl chlorides gave another set of non-conju-

gated dienes, 2-(o-vinylphenoxy)ethyl methacrylate and

acrylate. Radical or photo-polymerization of the methacry-

late and acrylate yielded polymers which were soluble in

most of the polar organic solvents and had extremely high

melting points. Spectroscopic evidence showed that these

polymers contained only a very small degree of unsaturation.

All the evidence suggested that these polymers consisted

essentially of cyclic repeating units, which were presumably

ten-membered rings.















CHAPTER I
INTRODUCTION

General Background

(2-Vinyloxyethoxy)styrenes (I) were first synthesized

along with their 6-nitro analogs, (2-vinyloxyethoxy)-8-

nitrostyrenes (II), by ThompsonI in 1962: Nash2 had earlier

attempted the synthesis of o- and p-(2-vinyloxyethoxy)-B-

nitrostyrenes. These styrene derivatives were prepared at

that time for two purposes: (1) studies on their interesting

molecular properties and (2) their suitability as ideal models

for two-stage polymerization. Thompson finished, however,

only the first goal and left the second part pending.


,NO2
HC=CH2 HC=C


Q OCH2CH2OCH=CH2 OCH2CH2OCH=CH
2^^ OCC 2- 2 2
o-, m-, and p- o-, m-, and p-

(I) (II)
It was not until 1971 that Schwietert3 studied the two-

stage polymerization of the (2-vinylocyethoxy)-3-nitro-

styrenes via independent anionic and cationic initiation.

Studies on the polymerization of the (2-vinyloxyethoxy)-

styrenes, not yet undertaken, provided an interesting









research subject, which was undertaken by the author when

he entered the University of Florida in 1970.

The prior literature concerning the objective studies

of the title compounds (I) and their related derivatives

will be described in the following sections as: (a) two-

stage polymerization, (b) chemical reactions of polymers,

and (c) cyclopolymerization of unsymmetrical dienes.

Although these subtitles appear to be different, they are

actually related to each other as a whole for the title

compounds under investigation.

Two-Stage Polymerization

The industrial importance of two-stage polymerizations

has been demonstrated in the vulcanization of rubber, and in

the thermosetting of phenol-formaldehyde, urea-formaldehyde,

and alkyd polymers. In the area of vinyl polymerization,

Mark4 has first shown that when vinyl n-propyl ketone is

copolymerized with 10% of vinyl allyl ketone, linear polymer

chain-molecules are formed primarily through the more readily

polymerized vinyl group only, leaving the less reactive allyl

groups intact. Butler and his coworkers5-7 demonstrated

later that allyl ethers of allyl substituted phenols and

vinyl ethers of unsaturated alcohols could be polymerized

selectively via cationic initiation to give thermoplastic

polymers containing residual unsaturated groups. The result-

ing linear polymers, which possessed the allyl-type double

bond, were then crosslinked or thermoset by radical initia-

tion. A typical reaction sequence is shown in Equation (1).









CH2=CH -(CH2CH)n --CH2CH n
0 0 0
CH2 CatiCH
CH2 Cationic CH2 Radical CH (1)
CH2 ------ CH L2
0 0 0
CH2 CH, CH2
CH2=CH CH2=CH --CH2CH-
Crosslinked
Polymer

After the reactivity of many of the important olefinic

monomers toward radical or ionic initiation became clear,8

more investigations on a variety of non-conjugated diolefins

appeared. Among these works, B-vinyloxyethyl methacrylate

was reported to react differently to cationic and anionic

initiations, yielding soluble polymers of different struc-

tures-0 Similarly, it has been shown that allyl metha-

crylate and acrylate were polymerized with typical anionic
11-13
initiators and with lithium dispersion in tetrahydro-

furan4 to provide soluble polymers having essentially the

same structure, comprising a polymethacrylate or polyacry-

late backbone with pendent allyl groups. In addition, a

few para-substituted styrenes have been polymerized anion-

ically15 or cationicallyl6 to linear polymers. Subsequent

polymerization across the pendent vinyl or acetylenic

groups always led to crosslinking the system.

More recently, Schwietert2 polymerized (2-vinyl-

osyethoxy)-B-nitrostyrenes selectively through the nitro-

vinylic moiety or the vinyl ether moiety via anionic or

cationic initiation, respectively. The resulting linear

polymers obtained from cationic initiation were subsequently


I









crosslinked through the pendent B-nitrovinyl groups by

anionic polymerization. The reaction sequence is shown in

Equation (2). The o-isomer could not be anionically poly-


/NNOO N2 NO2
HC=CH HC=C CHCH-



S Cationic Anionic (2)
0 < 0 > 0
CH2 CH CH2
CH2 CH2 CH9
0 0 0 -
--fCCHCH2*n CH=CH2 CH=CH2

o-, m-, and p- o-, m-, and p- m- and p-



-Anionic -> Crosslinked polymers Air

merized under the same conditions as those of the m- and p-

isomers. Evidence was presented to support the conclusion

that the pendent vinyloxyethoxy group exerted an "ortho

effect," which was believed to be a steric effect, on its

adjacent B-nitrovinyl group, thus preventing the polymer-

ization.

Chemical Reactions of Polymers

Long since the nitration of cellulose was conducted in

1854, the chemical reactions or chemical modifications of

polymers have been an important branch of synthetic polymer

chemistry. In general, most synthetic reactions of polymers

are carried out for two purposes: (1) preparation of poly-

mers with special functional groups or (2) modification of

the polymer backbone chain in order to achieve special or




5




unusual effects not readily obtainable in polymerization

reactions. The nitrated cellulose or cellulose nitrate,

which is known for its much greater endurance and impact

resistance in many respects than cellulose itself, served

as a good example of the first objective. On the other

hand, poly(vinyl alcohol) (III), which is a typical well-

known example of a polymer whose monomer does not exist,

exemplifies the second purpose.


-(CH2H)n-
(CH3CO20 =0
CH3

(IV)



--fCH2CHn C H CHO 2 0
OH

(III) C3H
(V)


CH2CHHCNI Q-
> CH2CH2CN

(VI)

Poly(vinyl alcohol) with its free hydroxy groups offers

considerable versatility for chemical transformation.1 For

example, it it capable of undergoing esterification to its

parent poly(vinyl acetate) (IV) and many other polyesters,

acetal formation to poly(vinyl butyral) (V), and cyanoethy-

lation with acrylonitrile to poly(vinyl -cyanoethyl ether)

(VI).









Cyclopolymerization of Unsymmetrical Dienes

The polymerization of non-conjugated dienes generally

resulted in the formation of either linear polymers contain-

ing unreacted double bonds or crosslinked polymers. Butler

and his coworkers1819 first found that several diallyl

quaternary ammonium salts polymerized to yield soluble and

hence linear polymers containing little or no residual un-

saturation, and involving an alternating intramolecular-

intermolecular chain propagation. To describe this new

polymerization reaction, the term "cyclopolymerization"

has now been adopted. Since then, a great number of related

papers have emerged and the new field has rapidly developed.

A general reaction mechanism is shown in Equation (3). When



S N R* R R (
-(3)

(VII) (VIII) (IX) n


a suitable initiator reacts with one double bond of a diene

monomer (VII), a anion, cation, or free radical-containing

intermediate (VIII) is formed. This intermediate then

reacts intramolecularly with the remaining double bond to

close the ring and produces a different reactive species

(IX). The reaction propagates by attacking another monomer

molecule and performing repeatedly, leading eventually to a

linear, saturated polymer comprised of cyclic repeating

units.








After Butler's initial investigations, it was soon
demonstrated that a variety of symmetrical 1,5- or 1,6-
dienes could be polymerized to soluble saturated polymers.
Their structures were mainly composed of five- or six-
membered rings with methylene groups alternating along the
linear polymer chain. A few typical examples, such as the
disubstituted 1,6- and 1,7-heptadienes (X),20-23 1,2-di-
vinylbenzene (XI),24 and acrylyl and methacrylyl anhydride
(XII),25 are shown as follows.
(XII), are shown as follows.


H2C R H2 R

(CHi2)n

n = 2, R = H, CO2CH3, or C6H5
n = 3, R = H, CO2CH3, or C6H5

(X)


Od


R R

(CH2 n
-n


(XI)


R R




R = H or CH3
(XII)


R R



n








Symmetrical non-conjugated dienes, which were separated

by more than three atoms, showed less tendency to form cyclo-
26
polymers. Holt and Simpson studied the polymerization of

a series of diallyl esters (XIII) by radical initiation.


H2C=CHCH202C-(CH2)n-CO2CHCHCH=CH2 C02CH2CH=CH2


n =0-8
nCO2CH2CH=CH2

o-, m-, and p-

(XIII) (XIV)

They found that the intramolecular reaction did occur

although the degree of cyclization was low. The three

isomeric diallyl phthalates (XIV) were also studied.

Diallyl terephthalate turned out to be crosslinked after

the polymerization. Under the same reaction conditions,

the o-isomer way cyclized to 41% and gave a soluble polymer.

The explanation was that "a minimum of ten atoms was required

for ring-closure between substituents on para positions."
27
Schulz and Stanner studied the polymerization of three

isomeric bis-N-vinyl compounds (XV). Similar to the pre-

vious case (XIV), the p-isomer was crosslinked while the o-

isomer was polymerized to a soluble product with 70%

cyclization. Recently one more example was demonstrated by
0 0
II II
OCNIICH=CH2 OCCH=CH2


OCNHCH=CH2 -OCCH=CH
0 0
o-, m-, and p- o-, m-, and p-
(XV) (XVI)








Azuma and Ogata.28 They studied the polymerization mech-

anism of three isomeric diacrylates (XVI) by radical and

photo-initiation, finding that only the o-isomer yielded

a soluble polymer.

In the literature, it was found that polymerization

studies of unsymmetrical non-conjugated dienes were limited
29
to six-membered and smaller ring formation. Butler et al.2

studied the free radical polymerization of unsaturated

esters of maleic and furmaric acids (XVII), and found that
CO2CH
COACH 2 3
CO2CH -fCH2CH COxCH3 CH-CH-+-
SCH2 C=O
> o -H2
<^ ,^. 11 1 2
0 0 CH CH=CH2
CO2CH 3

(XVIII) x : y : z = 1 : 3 : 1

the polymerization of such unsymmetrical non-conjugated

dienes having double bonds of different reactivity resulted

in some cyclization. By stopping the polymerization just

before the gel point, a series of soluble polymers contain-

ing a considerable amount of cyclization (23-63%) were

obtained. Schulz et al.30 prepared a 1:1 copolymer (XX) of

allyl alcohol and acrylic acid by hydrolysis of the cyclo-

polymer (XIX) obtained from allyl acrylate (XVIII). Since

alternating copolymers could not be synthesized from direct

copolymerization of the monomer pairs, cyclopolymerization

of the unsymmetrical dienes would give rise to a new route

to the synthesis of alternating copolymers, which would be

otherwise unobtainable.




10






CH
0 0 0 00 'OOH O2
Sn

(XVIII) (XIX) (XX)
31,32
Trossarelli et al.3132 studied the radical polymer-

ization of a series of unsymmetrical dienes mechanistically

including allyl acrylate, allyl methacrylate, N-allylacryl-

amide, N-allylmethacrylamide, and vinyl crotonate. They

found that these unsymmetrical dienes could be polymerized

to soluble polymers containing appreciable amounts of cyclic

units under suitable reaction conditions. In addition, they

derived a general kinetic scheme for chain propagation of

radical polymerization of unsymmetrical dienes, A-B, as

follows.

(i) Intramolecular chain propagation reactions (cyclization)


--A. B k
._.1 A-B-

--B. A k
2 _--B-A"

(ii) Intermolecular chain propagation reactions

- B-A- + A B k3 -B-A-A. B


- B-A. + B A k4 -BA-B A
4L --B-A-B' A


- A-B- + A B k
) --A-B-A. B


- A-B. + B A k6 -A-B-B A
K6 --A-B-B A








-- A. + A B k
(* + A, B 7 --A-A B


-A. + B A kA
B + /A -A-B- A


- B + A B k9 -B-A B

A AA

-- B. + B A kA
(10 -B-B- A
(A \ 0 A

The arrangements of the structural units along the chains

should be determined essentially by the relative rates of

the above kinetic scheme assuming that the reaction charac-

teristics of the growing polymer radicals depend primarily

on the unit at the growing end and not on the length and

composition of the chains. Under some basic assumptions,

two meaningful equations, (4) and (5), were derived, where


fA ac(M +B)
f (4)
B (M +y)


fL (fA + fB) (aM2 + bM)
-- + --- (5)
'C (fAc+ Bec (M + c)

fA' fB fAc' and fBc are the respective mole fractions in the
increment of a polymer being formed at a given stage in the
-B-
polymerization of the two linear structural units, A and
-A-
, and the two cyclic structural units, -B-A- and -A-B-;
kB/ I
M is the monomer concentration; a,B,y and a, b, c are con-

stants composed of rate constants; fL/fC is the ratio









between the mole fractions of the linear and the cyclic

units formed from the diene, A-B.

Equation (5) clearly predicts that the ratio fL/fC

will decrease with decreasing monomer concentration. In

other words, fC will increase at the expense of fL, i.e.,

polymerization tends to intramolecularly cyclize first, and

then followed by intermolecular propagation.

It seems clear that for unsymmetrical dienes, the

highest degree of cyclopolymerization could be achieved,

first, from monomers having double bonds of comparable

reactivity toward copolymerization but with little tendency

to homopolymerize, and secondly, by diluting the monomer

concentration and stopping the polymerization at low con-

cenversion to prevent it from going beyond the gel point.

Research Objectives

The purpose of this research work was first to study

whether the (2-vinyloxyethoxy)styrenes (I) could be success-

fully polymerized by means of two-stage polymerization. It

would be important to understand the reactivity of the two

different double bonds, the styryl and the vinyl ether,

involved in the molecules under study. It is known that

styrene and methoxystyrenes are susceptible to anionic,

cationic, and free radical initiations and vinyl ethers are

only susceptible to cationic initiation.8 With all the

previously described precedents examined, it was foreseeable

that the (2-vinyloxyethoxy)styrenes would be capable of


_~








being polymerized through only the styryl double bond by

appropriate anionic initiators while leaving the vinyl ether

moiety unreacted. The expected linear polymers thus formed

could be crosslinked via the pendent vinyl ether groups by

cationic initiation. In contrast with their B-nitro analogs,

the (2-vinyloxyethoxy)styrenes would form crosslinked polymers

by starting with cationic initiation, because the styryl

double bond is as susceptible to cationic initiation as is

the vinyl ether group while the B-nitrovinyl group is not.

Provided that the (2-vinyloxyethoxy)styrenes could be

polymerized through only the styryl double bond, the pendent

vinyl ether groups on the polymer side-chains would remain

intact and the polymer would be linear and thus soluble.

Since vinyl ethers are known to undergo many chemical
33
reactions,33 the vinyl ether groups on the polymer side-

chains are expected to behave similarly. One of the most

interesting reactions seemed to be the hydrolysis of the

vinyl ether in the presence of a catalytic amount of acid

to its corresponding alcohol and acetaldehyde. 37 A

general equation is shown in Equation (6). By this means,


R-O-CH=CH2


H30 R-O-H + CH3CHO
3


(6)


the vinyloxy-containing polymer could be converted to a

hydroxy-containing polymer if a suitable solvent could be

found. The new polymer thus generated having a potentially

reactive hydroxy group would be an interesting new material

to study; for instance, it should be capable of undergoing









a great number of reactions similar to those reported

earlier with poly(vinyl alcohol).7

In addition to being prepared from the hydrolysis of

the poly-(2-vinyloxyethoxy)styrenes, the polyhydroxyethoxy-

styrenes or more correctly, polyvinylphenoxyethanols, might

also be obtained from their monomers by direct polymerization.

The monomeric vinylphenoxyethanols could be prepared from

the acid-catalyzed hydrolysis of the (2-vinyloxyethoxy)-

styrenes. Contrary to vinyl alcohol, which virtually does

not exist, the vinylphenoxyethanols are vinyl aromatic

alcohols and should be stable enough to be isolated. Sur-

prisingly, a literature survey revealed merely two related

examples, p-vinylphenylethyl alcohol38 and p-vinylphenyl-

alkylcarbinols,39 along with their respective polymers.

Therefore, the synthesis of the monomers themselves would

be an interesting work.

If the vinylphenoxyethanols are available, more

interesting work might be undertaken along this line in

view of the great versatility for chemical transformation

offered by the reactive hydroxy group. By reacting with

acrylyl chloride, the vinylphenoxyethanols could be converted

to their corresponding acrylates. In contrast with the

(2-vinyloxyethoxy)styrenes in which the two unsaturated

double bonds have extremely different reactivity ratios in
40
radical copolymerization, the two unsaturated double

bonds in the vinylphenoxyethyl acrylates, i.e., the styryl

and the acrylic, have fairly similar reactivity ratios.41


1




15




As previously mentioned, when the two unsaturated double

bonds of an unsymmetrical diolefin have comparable react-

ivity toward copolymerization, they tend to cyclopolymerize.

Besides, the literature has not revealed any example of

large-ring cyclopolymers made from unsymmetrical dienes that

are separated by more than three atoms. Hence, the attempt

to synthesize and cyclopolymerize the vinylphenoxyethyl

acrylates, particularly, 2-(o-vinylphenoxy)ethyl acrylate,

which would be structurely favorable, seemed to be very

challenging.


I














CHAPTER II
RESULTS AND DISCUSSION

Synthesis and Polymerization of
o-, m-, and p-(2-Vinyloxyethoxy)styrenes

Synthesis of o-, m-, and p-(2-Vinyloxyethoxy)styrenes

The (2-vinyloxyethoxy)styrenes (I) were prepared

essentially according to the methods given by Thompson1

with only minor modification. A general reaction scheme is

shown in Equation (7). The hydroxybenzaldehydes (XXI) were

CHO CHO CHO
SKOH C1CH2CH20CH=CH 2

OH -O-K+ 0
CH2 (7)
o-, m-, and p- CH2
0
(XXI) (XXII) HC=CH2

(XXIII)
HC=CH2

(C6H) 3PCH Br5 n-BuLi 02
(XXIII)

CH.
CH
0z
HC=CH2

o-, m-, and p-

first converted to their respective potassium salts (XXII)

by treating with an equivalent amount of alcoholic potassium

hydroxide. The potassium salts were hygroscopic and had to

be dried thoroughly in a vacuum oven before use. The second









step of the reaction was carried out nicely in N,N-dimethyl-

formamide (DMF) under mild reaction conditions. The (2-vinyl-

oxyethoxy)benzaldehydes (XXIII) were obtained in good yields

(70-80%). The Wittig reaction 43 was employed to accom-

plish the last step conversion. Ortho- and m-(2-vinyloxy-

ethoxy)styrene were liquids at ambient temperature and their

boiling points were only slightly lower than those of their

corresponding benzaldehyde precursors at reduced pressure.

Therefore, their purification by fractional distillation

was best achieved by using a high efficiency spinning band

column to assure the highest possible purity and yields.

Like styrene, these styrene derivatives were also thermally

unstable compounds. During the distillation period, the

crude products became viscous and obviously had polymerized

to some extent even though an inhibitor was used. Cuprous

chloride was the most effective inhibitor among those tested;

its extremely high boiling point (13660C) caused no contam-

ination of the products. The yields of this step were low

(30-40%). The physical properties of the (2-vinyloxyethoxy)-

styrenes agreed very well with those obtained by Thompson.

The NMR spectra of o-, m-, and p-(2-vinyloxyethoxy)styrenes

are shown in Firgures 1, 2, and 3, respectively.

Anionic Polymerization of o-, m-, and p-(2-Vinyloxyethoxy)-
styrenes

All three isomeric monomers were polymerized success-

fully through use of sodium naphthalene radical anion 47

in tetrahydrofuran (THF) at low temperatures. A general re-






300 200 0 H


I
ii

ULJkAJw


HC=CH 2
0 ^OCH2CH2OCH=CH2


.. .. ... . 1 I i , I . I . .
8 0 7.0 6.0 5,0 PPM ( 4.0 30 20 00
Figure 1. NMR Spectrum of o-(2-Vinyloxyethoxy)styrene


r


I















HC=CH2



OCH2 CH20OCH=CH2


8.0 7.0 6.0 5.0 PPM ( A 4.0 3.0
Figure 2. NMR Spectrum of m-(2-Vinyloxyethoxy)styrene



























U




0


CNI
UU
Ii
0I 0


Q)





4 x,
r4













4-4
0






















4-1
u
Q)
C)
4-






























CN
CJ




|C; CN
+N C)i
U
C)C

rxl J^
C)r
C) 0
U O


a)




0
si Cf




c
0

4-a












U
S a)
C



























Q-)
a)
0






ow









action sequence is shown in Equation (8). In the case of

HC=CH2 -CHCHCH2
^2 Z n 4CHCH)--

S Anionic or Cationic -(8)
radical 0 0(
CH, CH CH2
i2 2
CH2 CH2 CH2
0z 0 0
HC=CH2 HC=CH2 -CH2CH-

o-, m-, and p- (XXIV) Crosslinked
polymers

the p-isomer, -500C seemed to be the lowest optimum temper-

ature. At temperatures lower than -50 C the p-isomer pre-

cipitated out of the solvent even though the solution concen-

tration was fairly low (approx. 10%). After polymerization,

the polymeric o- and p-isomers were isolated and purified

as white powdery solids. The m-isomer, however, formed a

soft gum, although its molecular weight was comparable to

those of the o- and p-isomers. The soft appearance of the

polymeric m-isomer was probably due to its glass-transition

temperature which is lower than ambient temperature. The

poly-(2-vinyloxyethoxy)styrenes (XXIV) were high molecular

weight linear polymers as indicated by their molecular weight

and great solubility in most common organic solvents. With

respect to the solubility characteristics of these polymers,

they were found to be soluble in benzene, carbon tetrachlo-

ride, chloroform, 1,4-dioxane, N,N-dimethylformamide, tetra-

hydrofuran, etc., but they were insoluble in diethyl ether,

methanol, and petroleum ether. It should be noted that the

o- and m-isomers yielded stable polymers which did not change








their solubility in air over a long period of time. The

polymeric p-isomer was, however, very unstable in air and

became partially insoluble within a short period of time

(a few days), presumably caused by air oxidation through the

unsaturated vinyl ether moiety on the polymer side-chains

thus leading to crosslinking. The partially soluble poly-

meric p-isomer was extracted with benzene and the insoluble

particles were filtered off to give a clear solution.

Reprecipitation from low-boiling petroleum ether yielded

up to 40% of the original weight of the polymer. It was

very surprising that this 40% soluble part could stay in air

without changing its solubility as long as the polymeric o-

and m-isomers, yet the cause was not clear. Since the

insoluble part of the p-isomer had nearly the same infrared

absorptions and softening point as the soluble portion, it

appeared that the insoluble part of the polymer was only

slightly crosslinked. The physical properties of these

anionically initiated polymers are shown in Table 1.

The conclusion that anionic polymerization occurred

only through the styryl double bonds of the (2-vinyloxy-

ethoxy)styrenes was also supported by spectroscopic evidence.

The NMR spectrum of poly[p-(2-vinyloxyethoxy)styrenej is

shown in Figure 4 (page 21), as an example, in comparison

with that of its parent monomer (see Figure 3, page 20).

The infrared spectra of the polymers lacked the absorptions

at 1420 and 910 cm1, characteristic of the C-H bend of the

styryl double bond, but the absorptions at 1640, 1620, 1200,













r-l
I

I H


S-4








0 t
U0 0 0
H U










I 0
U
-N--




I C







4 0U



E0





















SO
0 O
So








0



0c-
*d 0 S


co0





0





O








0
Q

o


O O0 C) O0 CO
r-4




CO CO ir LC4 L)
I I I I I


In' 0 'i





I-I
HH
H H H


U4

0

04C
rU)




N
H


o ,




00 4-
0 01
S4-3













o a

0I
4r-
CO
(< M





o








0c
4-


'-4

C)


0

*-D
0

U

C4
r4



















0
>,

"o
















wo
c0
,3)

























H bo





o
E(


cn 0







-l
and 815 cm characteristic of the vinyl ether double bond,
-I
were still present. Whether the absorption at 1625 cm ,

characteristic of the C=C stretch of the styryl double bond,
-i
and the absorption at 990 cm1, characteristic of the C-H

out of the plane bend of the styryl double bond were still

present, could not be verified due to the interference by the

adjacent strong vinyl ether absorption bands. The ultra-

violet spectra of the polymers were different from those of

their corresponding monomers. The K bands, caused by the

styrene moiety of the monomers in the region of 250-260 nm

disappeared in the polymers. The B bands, typical of benzene

nuclei containing auxochromophores, were shifted from 290-

300 nm in the monomers to 275-235 nm in the polymers. The

blue shifts clearly indicated that the polymeric molecules

were less conjugated than their respective monomeric mole-

cules. The absorption maxima (Xmax), molar absorbance (A.),

and molar absorptivity (e) of the monomers and of the poly-

mers are listed in Table 2. The ultraviolet spectra of the

polymers are compared with those of their respective poly-

mers as shown in Figures 3, 4, and 5.

Characterization of the Poly-(2-vinyloxvethoxy)styrenes

The poly-(2-vinyloxyethoxy)styrenes obtained by anionic

initiation were well characterized. In addition to the

routine intrinsic viscosity measurements, each polymer was

characterized by molecular weight determination and gel

permeation chromatography. The data are shown in Table 1,










Table 2

Tabulation of Maxima in Ultraviolet Spectra


Compound Cone., a A. l
5 max max max
M. x 10 nm x 10-


o-(2-Vinyloxy- 5.87 248 0.667 1.14 4.06
ethoxy)styrene 300 0.236 0.402 3.64

m-(2-Vinyloxy- 8.32 249 0.89 1.07 4.03
ethoxy)styrene 295 0.20 0.240 3.38


p-(2-Vinyloxy- 2.00 261 0.51 2.55 4.41
ethoxy)styrene 10.00 290 0.28 0.280 3.54

301 0.17 0.170 3.23

Poly[o-(2-vinyl- 20.3 273.5 0.42 0.207 3.32
oxyethoxy)styrene] 279.5 0.37 0.183 3.26

Poly[m-(2-vinyl- 45.6 273.5 0.885 0.194 3.29
oxyethoxy)styrene] 279.5 0.81 0.178 3.25

Poly[p-(2-vinyl- 40.8 277.5 0.66 0.161 3.21
oxyethoxy)styrene] 285 0.55 0.135 3.13


a. Molar concentration of the solute in


1,4-dioxane


b. Calculated by the Beer-Lambert Law, A = Ecb



























X?


u
x
0




0
x





l)




U




r >-\
y j


r-4
r-4

U



10











oa
0


O

0 O





N
O
o o





0 *






0t
S4
0 X
o o






m 0






4J
o rh'd













-:

















4L4
b0r
*^l
ctr


CO t- to Q I O N I -
d d o do d do

30NVByOSBV












-4




0






.0



4-J


W
~o-O~O















'-0
O cc
0 4J










n o








I 4-J



Nl 0 4
co 0




N 0 w
116 n in P.a,
0 w cli C -















0



00 w
*H 4J




41 -r-4











1-4 f

0
0) ( N
co LOm











S0 0 0 0 0 0 0
II :I










3""NV880SGV o
.r4
rt41
























II





0













-4
0 Co.
















4 o














a 0 ua

a C


U 0 o)
o


~1 u C)
~~c'~J


C







)r-

> 0


0 0


4-1



4 4-1
X 0
E >.-


S> 4
Z IQ

w L 0


4-1
0 -0
QC)

4-1


0 z
C.H



D
*H U








rC

Q)



44~


CO 0 0 0 0 o 0 J -0
d d d d d d d d

33NV8tJOS8v








page 24. Molecular weight determination was measured by

membrane osmometry, hence the molecular weight obtained was

the number-average molecular weight, M These polymers had

fairly high molecular weights ranging from 9 x 104 for the

p-isomer to 2.5 x 105 for the o-isomer.

The number-average molecular weight of a polymer is

theoretically calculable if the polymerization is obtained by

anionic initiation without chain termination, i.e., "living"

anionic polymerization.48 Equation (9) is suitable for an-

[Monomer] 2[Monomer]
M = ------ = ------ (9)
n -[Catalyst] [Catalyst]

ionic polymerization via a bifunctional chain propagation
44
mechanism; for example, the polymerization of styrene by

sodium naphthalene in tetrahydrofuran at low temperature.

Equation (9) should be applicable to the present system as-

suming the polymerization of the (2-vinyloxyethoxy) styrenes

did follow the bifunctional propagation mechanism. Since

the mechanism of the anionic polymerization with sodium naph-

thalene iswell known and all the phenomena characteristic of

the "living" polystyryl propagating anion and the near 100%

conversion were observed, the assumption seemed to be very

reasonable. According to Equation (9), the calculated M's
n
were 4.3 x 10 for the o-isomer, and 1.4 x 10 for the p-

isomer. Compared with the true M determined by membrane

osmometry, the calculated values were only about 20% as much









as the true values. This would appear to indicate that

merely 20% of the added initiator was actually involved in

the polymerization; the remaining 80% could have been

either destroyed or not reacted at all. Morton and
45
Milkovich45 have studied homogeneous anionic polymerization

of styrene in tetrahydrofuran using sodium naphthalene as an

initiator, and found an average initiator loss about 50%

after mixing the initiator, solvent, and monomer. Among the

initiator losses, they estimated that approximately two-thirds

was lost even before adding the monomer; the following add-

ition of the monomer accounted for the remaining one-third

loss. In their studies Morton and his coworker, using

very subtle vacuum line techniques, could not prevent 50%

initiator loss through termination by impurities. By com-

parision, the 80% loss obtained here, which was presumably

caused by less subtle vacuum line techniques, should be

reasonable and acceptable, at least from the standpoint of

the synthetic approach.

Molecular weight distribution of the polymers was

determined by gel permeation chromatography (GPC). 50

The results showed that the o- and p-isomers gave fairly

narrow distribution curves and accordingly had a value of

S/Mn close to unity. The m-isomer, however, gave a some-

what broader distribution curve and showed no improvements

after further attempts to synthesize it. The difference in

molecular weight distribution between these isomeric polymers









is presently not clear, but it was suspected that the

difference was probably caused by their difference in re-

activity and the not very subtle techniques used. The

molecular weight distribution curves of the three isomeric

poly-(2-vinyloxyethoxy)styrenes are shown in Figures 8, 9,

and 10, respectively.

Radical Polymerization of o-, m-, and p-(2-Vinyloxyethoxy)-
styrenes

It was a little surprising that the (2-vinyloxyethoxy)-

styrenes also yielded linear polymers via free radical ini-

tiation. Although vinyl ethers could not be homopolymerized
8
by radical initiators, they have been reported to copoly-

merize with many other vinyl monomers,40,50-54 such as

acrylonitrile, methyl acrylate, styrene, vinyl acetate, vinyl

chloride, etc. The reactivity ratios of vinyl ethyl ether

(Ml) and styrene (1M2) were rl=~0 and r2=>50, respectively.40
The extremely different reactivity ratios of the vinyl ether

and styrene indicate that once a vinyl ether monomer rad-

ical (MI*) is formed, it tends to react with a styrene mole-

cule rather than to react with another molecule of its own;

on the contrary, a styrene monomer radical (M2-) tends to

react with another styrene molecule.55 As a result, one may

predict that the polymer formed at low conversion must

essentially consist of styrene units. However, the vinyl

ether could be incorporated into the polymer chain to some

extent if the polymerization were allowed to proceed to high

conversion. The only reasonable explanation seemed to be













































I I I I I I I I I I I I


19 21 23 25
COUNTS


27 29 31


Figure 8. Molecular Weight Distribution Curve
of Poly[o-(2-vinyloxyethoxy)styrene]




34



































19 21 23 25 27 29 31
COUNTS
Figure 9. Molecular Weight Distribution Curve
of Poly[m- (2-vinyloxyethoxy)styrene]











































19 21 23 25 27 29 31 33
COUNTS
Figure 10. Molecular Weight Distribution Curve
of Poly[p-(2-vinyloxyethoxy)styrene]




36




that the vinyl ether moiety in the (2-vinyloxyethoxy)-

styrenes was initiated too slowly to compete with the

styrene moiety and thus acted negligibly upon crosslinking

the system even at the fairly high conversion.

The spectroscopic evidence and solubility character-

istics proved that the'vinyl ether moiety was intact. The

infrared spectra of the radically initiated polymers were

identical to those of the anionically initiated polymers.

The continued presence of the strong absorptions at 1640,

1620, and 1200 cm- due to the vinyl ether double bonds

eliminated any possibility that cyclopolymerization had

occurred. As expected, these radical-initiated polymers

had the same solubility characteristics as the anionic-

initiated polymers did. Their physical properties are

shown in Table 3.

As previously mentioned,2 o-(2-vinyloxyethoxy)-5-nitro-

styrene could not be anionically polymerized by sodium

ethoxide due to the ortho-vinyloxyethoxy substituent which

presumably exerted an "ortho effect" on its nearby B-nitro-

vinyl moiety. It should be noted that, contrary to its 6-

nitro analog, o-(2-vinyloxyethoxy)styrene could be polymer-

ized either anionically or radically as well as its m- and

p-isomers. Apparently the so-called ortho effect was not

present here in this molecule as far as the reaction conver-

sion was concerned. It is believed that it was the B-nitro

group that made the drastic difference in polymerizability

between the two structurely similar compounds.


I
























O
U c"I cN

SC0












w 0
QJ






4-J ,
00
.r4 oU) % .o % O


C W C _U U U
0 c 0
r- 4.J 0 0 0


,0 h O Z

o a) .4 0 z z Z

'rl I

*H -

I.-

-rr-
H 0






1-4

0 0






(0



o 0


0 cc cd
Z O0 P





0 ^ 0) r
S 0 S CL -2:




38




Post-Cationic Polymerization of the Poly-(2-vinyloxyethoxy)-
styrenes

The three isomeric polymers were further polymerized by

boron trifluoride in toluene at -780C. In order to achieve

possible ladder polymerization instead of crosslinking, the

cationic initiation was conducted at very low concentration

(approx. 1% w/v). The polymeric products were pale yellow

amorphous solids and did not melt below 3000C. They were

found to be insoluble in all solvents tested though they

occasionally swelled. Both the very high melting temper-

ature and the non-solubility characteristics indicated that

these polymers had very rigid, three-dimensional molecular

structure, i.e., they had been crosslinked.

The infrared spectra of the polymers showed the lack of

all the absorption bands typical of the vinyl ether moiety.

The lack of the vinyl ether absorption indicated that the

polymerization had gone to completion. The physical proper-

ties of these crosslinked polymers are shown in Table 4.

Butler and Ferree56 have studied the mechanism of cross-

linking poly[m-(2-vinyloxyethoxy)styrene] by photo-initiation.

Preliminary results showed that irradiations of the polymer

in the presence of acceptors, such as chloranil or tetra-

chlorophthalic anhydride (TCPA), in acetonitrile under dry

oxygen-free conditionsyielded rapid precipitation of cross-

linked polymers, which showed the same spectroscopic and

physical characteristics as the cationically crosslinked

poly[m-(2-vinyloxyethoxy)styrene].


























-J
U)
0




0

4-i




0
.ri
Cl)
0




O1
















0

*.r
4C1




c


























u
r-l
0





C-
0


0
4-i




0














0
0)
C
*^
'd
0r

4-

l?


u












O U
.-H


0 *-r-
r-4 r-
00







.-r-I
*.l 1R







u
0 0


CO



0





*494



O d
0 9



0
CO











C)
*H 0


















0 *J




0 c


-t oo co
01% co 00


r-4 r-4 r--
0 0 0
H H H0














O O O


S0













41 4-1 -4
l0 0 ce
o x p








Synthesis and Polymerization
of o-, m-, and p-Vinylphenoxyethanols

Polyvinylphenoxyethanols from Hydrolysis of Poly-(2-
vinyloxyethoxy)styrencs

As previously mentioned, Schwietert polymerized m- and

p-(2-vinyloxyethoxy)-B-nitrostyrenes with sodium ethoxide via

anionic initiation producing the corresponding linear poly-

mers. Although the pendent vinyl ether moiety on the poly-

mer side-chains was intact as evidenced by the continued

presence of its characteristic infrared absorption, those

polymeric products were reported to be unstable in air and

became insoluble in all solvents tried over a short period

of time. D'Alelio and Hoffend13 have reported a similar

finding with their polymeric styrene derivatives, which had

unsaturated substituents at the para position.

The poly-(2-vinyloxyethoxy)styrenes, which were prepared

by either anionic or radical initiation as described before,

were found to be quite stable in air as noted by their un-

changing solubility over a long period of time (more than

one-half year) except the p-isomer which gave only 40% of

the soluble polymer after standing in air for a few days.

The contrast in stability of the poly-(2-vinyloxyethoxy)-

styrenes and those reported examples was remarkable, but the

cause was not clear yet. In addition to the difference in

stability of the poly-(2-vinyloxyethoxy)styrenes and the

poly--(2-vinyloxyethoxy)- -nitrostyrenes, their solubility

characteristics were also different. While the former was









soluble in most common organic solvents, the latter was

reported to be insoluble in most common organic solvents

tried but was soluble in N,N-dimethylaniline and hexamethyl-

phosphotriamide (HXPA).

Both the unusual stability and great solubility made

the poly-(2-vinyloxyethoxy)styrenes suitable for chemical

reactions. They underwent acid-catalyzed hydrolysis nicely

in a mixture of 10% dilute hydrochloric acid and 90% acetone,

leading to the formation of polyvinylphenoxyethanols (XXV).

The hydroxy-containing polymers were identified by spectro-

scopic evidence and elemental analyses. Their infrared

spectra showed a strong broad absorption at 3400 cm-,

characteristic of the 0-H stretch, and the lack of absorp-

tionsat 1640, 1620, and 1200 cm-, characteristic of the

vinyl ether moiety. The ultraviolet spectra of the polymers

were, as expected, practically identical to those of their

polymeric precursors, the poly-(2-vinyloxyethoxy)styrenes.

The infrared evidence and the elemental analysis indicated

this polymer hydrolysis reaction to be complete. The NMR

spectrum of poly[(o-vinylphenoxy)ethanol] is shown in Fig-

ure 11, page 46, to compare with that of its monomer (see

Figure 12, page 47). A significant change, in many respects,


-- CH CH -}- -- CHCH -)-



O CH2CH2OCH=CI 2 OCH2CH20H

o-, m-, and p- o-, m-, and p-

(XXV)









in the physical properties was noticed when the poly-(2-

vinyloxyethoxy)styrenes were transformed into the polyvinyl-

phenoxyethanols. Besides the higher melting points and

greater intrinsic viscosities than their respective poly-

meric precursors, the hydroxy-containing polymers showed

only limited solubility characteristics. They were soluble

in some polar solvents such as dimethylformamide and di-

methylsulfoxide, but were not as soluble in others like

acetone, chloroform, methanol, and tetrahydrofuran, with

the exception of the o-isomer which showed much greater

solubility in these solvents than the m- and p-isomers.

They all were found to be insoluble in less and non-polar

solvents, such as benzene, carbon tetrachloride, and petro-

leum ether. Just like monomeric aromatic alcohols, these

hydroxy-containing polymers were completely insoluble in

water. Since dimethylformamide dissolved the polymers to

give very clear solutions, solution casting from dimethyl-

formamide solution could be used to make a clear, trans-

parent polymer film. The physical properties of the poly-

vinlyphenoxyethanols are shown in Table 5.

Synthesis of o-, m- and p-Vinylphenoxyethanols

Unlike poly(vinyl alcohol) whose monomer does not exist,

the polyvinylphenoxyethanols could also be obtained from

direct Dolymerization of their respective monomers, vinyl-

phenoxyethanols (XXVI). These monomeric compounds could be

prepared from hydrolysis of the (2-vinyloxyethoxy)styrenes.




43









-e
H








bC C'

CD) C Ln

So o
r- 0 i0 0


Od 0



o 0



0




S4 4; 4o o 4- c





v q / o o o/
PH c c cl
0





4 )H c- jC- ',


0 -1 P-4 0 Q) 04 Q)
,-- ( c> c> II > > > > II

)0
S 0 0 0O
Sa o o o,




.4-I


0 0 0o o 0






0 r 30 1 r0

0 cz CL C
r 4 -, rC
0 1 4-J 4-c I 4-i
P' )i ) Ji Ji a)










CH=CH2 CH=CH2



OCH2CH2OCH=CH2 OCH2CH20H

o-, m-, and p- o-, m-, and p-

(XXVI)

Acid-catalyzed hydrolysis of the (2-vinyloxyethoxy)styrenes

went to completion within a short time as noted by the lack

of the characteristic absorption bands of the vinyl ether

group in the infrared and NMR spectra of the crude products.

The crude o- and m-isomers were extremely high-boiling

liquids under ambient conditions. The first few attempts to

purify them by using regular micro-distillation apparatus

led to either failure or very low yields, because the

crude products thermally polymerized very rapidly in the pot

at the necessary high distillation temperature in vacuo,

although an inhibitor was always used. Short path molecular
-4
distillation on a high vacuum line (approx. 10 mmHg.) was

later tried and found to be very effective as indicated by

the much improved yields (~80%). The pure o-isomer crystal-

lized in the cooling bath and did not melt at ambient tem-

perature, but a further attempt to recrystallize it from low-

boiling petroleum ether was unsuccessful. The p-isomer was

isolated as a solid and could be recrystallized from low-

boiling petroleum ether very well.

The molecular structures of the vinylphenoxyethanols

were identified by spectroscopic evidence and elemental









analyses. The infrared spectra of these compounds showed
-l
in common a strong broad absorption at about 3400 cm,

characteristic of the 0-H stretch, but lacked the absorp-
-l
tions at 1640, 1620, and 1200 cm characteristic of the

vinyl ether moiety. Their NMR spectra showed a sharp

singlet around 63.0, characteristic of the hydroxy proton.

As expected, their ultraviolet spectra were nearly identical

to those of their respective precursors. The NMR spectra

of o-, m-, and p-vinylphenoxyethanols are shown in Figures

12, 13, and 14, respectively.

From the viewpoint of organic synthesis, the vinyl

ether group played substantially the role of a protective

functional group in the preparation of the vinylphenoxy-

ethanols. If the vinyl aromatic alcohols are to be synthe-

sized directly from their benzaldehyde analogs by the Wittig

reaction, the strongly basic ylide would react with the re-

active hydroxy protons. Therefore two moles of the Wittig

reagent are required to react with one mole of the (2-hy-

droxyethoxy)benzaldehyde, which would be very inconvenient

for large scale synthesis as well as lead to a waste of the

ylide. Since the vinyl ether group is known to be inert to

strong bases,57 the vinyl ether groups in the (2-vinyloxy-

ethoxy)benzaldehyde did not react with the ylide. The

following acid-catalyzed hydrolysis demonstrated that the

vinyl ether group could be easily and completely removed and

thus caused no contamination of the products. It is note-

















































0





0
OD











t
e~l r.
u--

rj


0




o











o
C0
,1





Q)



*r

:J
0. 0









S (U
Pc



U(

0





47


































o


4J




C
0
>-






0

*i







0.







CM
4C
r



















































0
cl

u


Oc 0

U

C) J


0








0 0
o




4-J
f U



































-4

0.
r4





v^

c^

2




4->
U,

P-











HL




49



































o
S 0










cl
O














0

0




o 0
rl




Ur


~_









worthy that this valuable utilization of the vinyl ether

group as a protective group for the alcohol against strong
58
base has not been cited in the known literature source.

Radical Polymerization of the o-, in-, and p-Vinylphenoxy-
ethanols

The vinylphenoxyethanols were polymerized via free

radical initiation to give their respective polymeric

products. The infrared spectra of these radically initiated

polymers were identical to those of the polymers obtained

from the hydrolysis of the poly-(2-vinyloxyethoxy)styrenes;

so were their solubility characteristics and melting points.

This clearly indicated that the polyvinylphenoxyethanols

could be either indirectly or directly prepared. A general

reaction scheme is shown in Equation (10). The physical

HC = CH2


HC = CH 2 -HC---CHn
SOCH2CH2H -- (10)



OCH2CH2OCH=CH2 -_ HC-CH2n OCH2CH20H



OCH2CH20CH=CH2


properties of the radical-initiated polyvinylphenoxyethanols

are shown in Table 6.

Chemical Reactions of the Polyvinylphenoxyethanols

The polyvinylphenoxyethanols could be converted to


















OI0 H
E-4


-H tn 00

-r 0 C, r- 0
r-4

0

cd




O *U
00
i k





0dr C

cch O
X 0

0 *1



or-4
O 5


cOcc

0 0
Qi 0







,--4
C'0
H OJ






r0 0r- c O
H *M 0 u

rl N k H 0 0

.,10 H .-- N %1 C

C0 I 0 0 0

-W (-0 C Fr F4









- oo !O Z o
1*4*



00




r Cd ) C Co
40 ,C r


0 c' C MC C io
S>0 >0 > 0

r-4'
O IC I u I
PcL CM (U C N1









many of their polymeric derivatives by reacting their hydroxy

functional groups with many known chemical reagents, such as

acid halides, isocyanates, acrylonitrile in the presence of

base catalyst, etc. A few typical reactions are described

as follows.

Reaction with 3,5-dinitrobenzoyl chloride. Upon reacting

with 3,5-dinitrobenzoyl chloride in the presence of pyridine,

the hydroxy-containing polymers were converted to their

respective dinitrobenzoyl esters as shown in Equation (11).


O C1 -(-CHCH2--
-0-CH--C2-- OCC n

+ 0 N -O NO (
+ 02N N2 O>H2CH20CN0
OCH2CH20H N

02N
O NO2

(XXVII)

The infrared spectra of these polyesters showed a strong

carbonyl absorption at 1730 cm1 and nitro group absorptions

at 1540 and 1340 cm1. No absorption in the region of the

hydroxy group was observable. The elemental analyses showed

that the found values were in good agreement with the cal-

culated values of the poly(vinylphcnoxyethyl 3,5-dinitro-

benzoates) (XXVII). The solubility behavior of these

polyesters was similar to that of their polymeric precursors.

They were soluble in dimethylformamide, and were modestly

soluble in other polar solvents, such as acetone, acetoni-





















C-C




bOO
S0 LV Cr)
) C\j it) C)

0) O I I

o H


0

4-
SI I

o 3 c>o oo c0

0









ro H
4-i 41





H c U HH 4l *r- (a4
0i > 00 3) 00




u0
r0-

















O


O- 0 0
(0 0 0 0 04 4

0 40l -




14 14- 1ri
r- Q)C e Ea














o a a
0 -
Pc 0 tg Pc









trile, chloroform, dioxane, ethyl acetate, and tetrahydro-

furan but were insoluble in benzene, carbon tetrachloride,

ethyl ether, and petroleum ether. Their physical properties

are shown in Table 7.

A few other polymer reactions were carried out with

the o-isomer as an example as shown in Equation (12).


CH =CHCN



- CHCH2 n
OHCH2CH20H C6H5NCO






\ CH2(C6H4NCO) 2
>----


-{ CHCH2
OCH2CH2OCH2CH2CN


(XXVIII)

-4 CHCHd -
OCH2CH2OCKN



(XXIX)

Crosslinked Polymer

(XXX)


(12)


Reaction with acrylonitrile.59'60 In the presence of a base

catalyst, sodium methoxide, the hydroxy-containing polymer

was converted to its cyanoethylated adduct by reacting with

acrylonitrile under mild conditions (40 C). Heating was

necessary because no reaction was observed when the reaction

was conducted at ambient temperature. The infrared spectrum
-i
of the polymer showed absorptions at 2250 and 1127 cm1

indicative of the presence of CEN and aliphatic C-O-C,

respectively. No absorption in the 0-H region was observed.

The physical properties of the polymer are shown in Table 8.


~~









Reaction with isocyanates. Phenyl isocyanate upon reaction

with the hydroxy-containing polymer yielded a polymer which

showed infrared absorptions at 3330, 3290, and 1550 cm-

characteristic of the N-H group, and absorption at 1650 cm-1

characteristic of the C=O group of the secondary amide. No

broad absorption band in the 0-H region was observed. The

physical properties of the polymer are shown in Table 8.

After being treated with an equivalent amount of

methylene bis(4-phenyl isocyanate), a solution of poly-[2-

(o-vinylphenoxy)ethanol] became gelled the following day.

The polymeric product thus obtained was found to be insol-

uble in all solvents tried. The infrared spectrum of the

polymer showed all the absorption bands characteristic of the

secondary amide, and absorption at 2250 cm-1, characteristic

of the residual isocyano groups. No 0-H absorption was

observed, an indication that the polymer was highly cross-

linked.

Synthesis and Cyclopolymerization
of 2-(o-Vinylphenoxy)ethyl Methacrylate and Acrylate

Synthesis of 2-(o-Vinylphenoxy)ethyl Methacrylate and Acrylate

The methacrylate and acrylate were prepared by ester-

ification of 2-(o-vinylphenoxy)ethanol with acrylyl and

methacrylyl chloride, respectively, as shown in Equation (13);

however, they were purified differently. 0

OH RR
R 0
CH=C-C-C1 ^ (13)


R = H or CH3
























0

















fi







-o
H 1
r4
O



























a)





0




E--
,.-4



C





ai
.'-




























0
Ir-



-I
0











*r-
rt
>,

*r-
}-


- Fn

60






















0E
- 1



























C












tr
0o









O-O
*H
























PL


10 i:T


o o















o
- N- I


















o 0
l1 co

o
0











o 0 A









o0 o-t I


















SX i
H


> H X

X-








During the preparation of the methacrylate, it was

found that an impurity was always present in the crude

products obtained from the different runs although meth-

acrylyl chloride had been freshly distilled before use.

This impurity could not be removed by evaporation under

high vacuum, and attempts to separate it from the desired

product by fractional distillation were unsuccessful, be-

cause the crude product had thermally polymerized in the

pot before the impurity could be completely removed. The

impurity seemed to be methacrylic anhydride as indicated

by its infrared and NMR spectra. Purification by column

chromatography was then tried and found to be successful

as indicated by the TLC analysis. Subsequent molecular

distillation on a high vacuum line yielded the pure product,

but the yield was quite low. The infrared spectrum of the

compound showed a strong absorption at 1720 cm-, character-

istic of the C=0 stretch, and at 1170 cm-, characteristic

of the asymmetrical C-0 stretch. No absorption in the 0-H

region was observable. The NMR spectrum of the compound,

which showed the absence of the hydroxy proton, is shown in

Figure 15.

In the case of the acrylate, the spectral analysis of

the crude product did not show the presence of any impurities.

It was simply purified by distillation on a high vacuum line

to give the pure product, but the yield was not satisfactory.

The molecular structure of this diene monomer was confirmed










by spectroscopic evidence and elemental analysis. The in-

frared spectrum of the compound showed a strong absorption
-l -I
at 1724 cm-1 due to the C=O stretch and 1185 cm- due to the

asymmetrical C-0 stretch. No infrared absorption corres-

ponding to the 0-H was observed. The NMR spectrum of the

compound is shown in Figure 17.

Cyclopolymerization of 2-(o-Vinylphenoxy)ethyl Methacrylate
and Acrylate

The methacrylate and acrylate were polymerized via free

radical or photo-initiation in tetrahydrofuran at 600C or

ambient temperature, respectively. The polymeric products

thus obtained were found to be soluble in chloroform,

dimethylformamide, tetrahydrofuran, etc., and were still

soluble after standing in air for a few months. The melting

points of these polymers were extremely high (>300 C).

Besides, the solid polymers showed somewhat crystalline

appearance; however, preliminary investigation by X-ray

diffraction did not reveal any crystallinity. The physical

properties of the polymers are shown in Table 9.

The infrared spectra of the polymers, obtained from

the methacrylate monomer, showed only a very small degree of

unsaturation as evidenced by the presence of a very weak

shoulder at 1630 cm-1 due to the C=C stretches of the

styryl and acrylic double bonds, and by the absence of any

absorption near 1410 cm-1 due to the =C-H bends of the styryl

and acrylic double bonds. The absorptions at 1000 and 900

cm-1, characteristic of the =C-H out-of-plane bends of the
cm characteristic of the =C-H out-of-plane bends of the









double bonds, were also hardly detectable. The infrared

spectra of the radical and photo-initiated polymers, being

compared with that of their monomer, are shown in Figure 19.

The NMR spectrum of the radical-initiated polymer, as shown

in Figure 16, showed the presence of two tiny peaks at 66.1

and 65.6 corresponding to the terminal protons of the metha-

crylic double bond, but the vinyl proton absorptions of the

styryl double bond were hardly distinguishable from the

noise. While the NMTR absorptions in the region of the

vinylic protons essentially disappeared, a broad absorption

in the region of saturated aliphatic protons appeared.

The spectroscopic analyses of the polymers, obtained

from the acrylate monomer, showed even less unsaturation

than the methacrylate polymers did. This was evidenced by

the barely observable absorptions due to the styryl and

acrylic double bonds in the infrared spectra, and the hardly

observable absorptions due to the vinylic protons in the NMR

spectra, as shown in Figure 20 and Figure 18, respectively.

All the evidence presented, both physical and spectro-

scopic, have indicated that these polymers consisted essen-

tially of the cyclic repeating units containing only a very

small degree of unsaturation on the polymer side-chains.

Although a quantitative determination of the degree of un-

saturation was not undertaken due to the limited amount of

the polymers available, it could be roughly estimated that

the total degree of unsaturation should not be greater

than 10% in accordance with the well-known instrumental




60







bL0



I 0

SO C



0) 0
Cd

0 ra '.o C cO
S-co





w pi

r 4


S4
43 4-1 k ^0
4- H C CP r




Cd -
S *4
4-4 '
00 Eu 0 ) 0 0





0
Eb- f' b
J0




















H H
( 44






H >
r-4 l z







00 0
o -co -











0 c





0OQ 0 0
C H H





















:>- < <
O U U Cd Cd
0 0 0






61
































cz
.C
CI














-t








0
4



















-)









Lf



-4
:j
r-4
"Ih






62
























QTJ
(0





rc
4-1
o




























4-i
LP

























0





-4
,-4
QJ
rd
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3>
i-





63
















0








co




0 0.




,- -


















4-.4
C)



o e






C






64




























4-


I-;
r-c






4J





0



0.
















*41
co



































-43
,-
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tc












.H
1z1
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>c



*-
CN


1-1

CLI





















































































(%) aOupqTumsu-pi


65








0

--0





U) 4


r4-

c
C 4 .



0




o *O O












o o >D
0
-to



1.










SU
Q)


















0 c
S O-
'-- 1-
pi*
4-4





U OW

o C
1 i
u 0 Q)








3 00


oo k
Q) C-4-'
C L)

UT 0








0
C a *)

0 U 0





0 H
cn kT




o C
C)
























-/-
SQJ
LUU




O cH
4O Nr
JO

r0 r-:




S 0
P1







00
a)


XI










C)O
o




0
o 0
0 0




0 k



) 0H


O V4-
) 00





o e c
0 C 0




ci






Q)
o kna4
C *
^2c 3+-
^-1*rl
0 4-) p

0 O
On 0
CM I-
h i -
0
XI .-
01k -
0 3 O0
0 3 i
0 }-< >'
r^ 1- /^-
C W


(~) a~ue~~Tmsuel~




67




detectability inherent in the infrared and NMR spectrometry.

A general reaction scheme is shown in Equation (14).


0







R = H or CH

R = H or CH3


(14)


Radical or hv


R = H or CH3















CHAPTER III
EXPERIMENTAL

Equipment and Data

A Beckman DK-2A double-beam recording spectrophotometer

was used to obtain ultraviolet snectra.

A Beckman IR-8 or a Beckman IR-10 infrared spectro-

photometer was used to obtain infrared spectra.

A Varian A-60 NMR spectrometer was used to obtain NMR

spectra using carbon tetrachloride (CC14) or deuterated

chloroform (CDCI3) as the solvent.

A Thomas-Hoover capillary melting point apparatus was

used to determine the melting points of solid monomeric

compounds, and the melting points reported are uncorrected.

A Fisher-Johns melting point apparatus was used to

obtain the melting points of polymeric materials.

A Waters GPC 300 gel permeation chromatograph was used

with calibrated polystyrene gel columns to obtain molecular

weight distribution data.

A Mechrolab 502 high speed membrane osmometer was used

to measure number-average molecular weight data.

A Cannon-Uhbelodhe semi-micro dilution viscometer

(75/K620) was used to measure intrinsic viscosities, and the

constant temperature bath was set at 300 unless otherwise

indicated.









A Hanovia 679-A-36 high pressure mercury vapor lamp

(450 watts) was used as an irradiation source for photo-

polymerization.

Elemental anlayses were performed by Galbraith Lab-

oratories, Knoxvill, Tennessee and by PCR, Incorporated,

Gainesville, Florida.

Source and Methods of Purification of Reagents

Salicylaldehyde (practical) was obtained from Fisher

and used without purification.

m-Hydroxybenzaldehyde (practical) was obtained from

Pfaltz & Bauer and used without further purification.

p-Ilydroxybenzaldehyde (practical) was obtained from

Eastman Kodak and used directly.

2-Chloroethyl vinyl ether (practical) was obtained from

Aldrich and purified by distillation under vacuum.

Methyltriphenylphosphonium bromide (reagent) was obtain-

ed from PCR and purified by drying over phosphorus pentoxide

(P205) in a vacuum oven at 1000C before use.
n-Butyllithium (15% in n-hexane) was obtained from MCB

and used directly.

Acrylyl and methacrylyl chlorides (reagent) were obtain-

ed from Aldrich and purified by distillation under nitrogen

before use.

Monomer Synthesis

Synthesis of o-, m-, and p-(2-Vinyloxyethoxy)styrenes

o-(2-Vin-yloxethoxy)benzaidehyde. The potassium salt of









salicylaldehyde was prepared on a 1.0 mole scale. To a

solution of 65.0 g. of 86.8 % potassium hydroxide in 500 ml.

of absolute ethanol in a 1000 ml. round bottom flask was

added a solution of 122 g. of salicylaldehyde in 100 ml.

of absolute ethanol. A spontaneous exothermic reaction

accompanied by the formation of precipitate was observed.

The solvent was removed through rotary evaporation at re-

duced pressure, and any residual moisture was removed via

the benzene-water azeotrope. The yellow crystalline solid

was then dried in a vacuum oven at 800C overnight. The

yield was essentially quantitative.

To a 1000 ml. three-necked round bottom flask equipped

with a thermometer, a mechanical stirrer, and a condenser

protected by a drying tube were added 160 g. of the potassium

salt, 116 g. (1.0 mole plus 10% excess) of 2-chloroethyl

vinyl ether, and 400 ml. of anhydrous N,N-dimethylformamide.

The reaction mixture was heated to 1000C and stirred at this

temperature for 6 hours. At the end of the reaction, the

mixture was cooled and then poured into 1500 ml. of water.

The aqueous mixture was extracted with 300 ml. portions of

diethyl ether three times, and the combined ethereal extracts

were dried over anhydrous magnesium sulfate.

The ether was evaporated through a rotary evaporator,

and the residual oily liquid was distilled under vacuum

yielding 151 g. (78%) of a colorless liquid: b.p.: 1140C/

0.17mmHg. The infrared spectrum and physical properties of









this compound agreed with those obtained by Thompson.1

The NMR spectrum (CC14) of the compound showed absorp-

tions at 610.4 (singlet, 1H, CHO), 7.8-6.8 (miltiplet, 4H,

aromatic H), 6.45 (quartet, 1H, OCH=), and 4.35-3.94 (multi-

plet, 6H, =CH2 & OCH2CH20).

o-(2-Vinlyoxyethoxy)styrene. The methyl ylide was generated

in situ as follows. In a 3000 ml. three-necked round bottom

flask equipped with an addition funnel, a mechanical stirrer,

a condenser protected by a drying tube, a gas inlet, and a

rubber septum were placed 122 g. (0.33 mole) of dry methyl-

triphenylphosphonium bromide and 1200 ml. anhydrous ether.

A gentle flow of dry nitrogen through the apparatus was main-

tained throughout the reaction. To the stirred ether suspen-

sion was added 235 ml. of n-butyllithium (15% in n-haxane)

by using a 30 ml. syringe. The nearly clear orange ylide

solution was formed at the end of the addition, and it was

continuously stirred for 2 hours.

To the ylide solution was slowly added a solution of

64.5 g. (0.33) mole of o-(2-vinlyoxyethoxy)benzaldehyde in

200 ml. of anhydrous ether. The pale yellow slurry thus

formed was stirred overnight. At the end of the reaction,

1000 ml. of water was added to the reaction mixture, and the

aqueous layer was extracted with 250 ml. portions of ethyl

ether three times. The combined ethereal solution was dried

over anhydrous magnesium sulfate. After removal of the sol-

vent on a rotary evaporator, the oily residue, in which a









small amount of cuprous chloride was added as an inhibitor,

was fractionally distilled under vacuum through a 60 cm.

spinning band column to yield 24.9 g. (40%) of a colorless

liquid; b.p.: 90-920C/0.70mmHg. The infrared and ultra-

violet spectra of this compound as well as its physical

properties agreed with those obtained by Thompson.1

The NMR spectrum (CC14) of the compound showed absorp-

tions at 67.43-6.55 multiplee, 5H, aromatic H & PhCH=),

6.38 (quartet, 1H, OCH=, J acis = 7 Hz, J trans = 14.5 Hz),

5.64 & 5.16 (AB quartet, 2H, =CH2, JAB = 1.7 Hz, JAX = 17.8

Hz, JBX = 11.0 Hz), and 4.25-3.72 multiplee, 611, OCH=CH2 &

OCH CH 20).

m-(2-Vinyloxyethoxy)benzaldehyde. This compound was prepared

from the potassium salt of m-hydroxybenzaldehyde and 2-chloro-

ethyl vinyl ether by the procedure given above for o-(2-

vinyloxyethoxy)benzaldehyde on a 0.6 mole scale. Vacuum

distillation of the crude product gave 81.9 g. (71%) of the

product; b.p.: 88-900C/0.07mmHg. The liquid crystallized

on standing and could be recrystallized from n-pentane to

give a white crystalline solid; m.p.: 41.5-420C.

The NMR spectrum (CC14) of the compound gave absorp-

tions at 69.90 (singlet, 1H1), 7.40-6.98 multiplee, 4H),

6.43 (quartet, 1H), and 4.35-3.87 multiplee, 6H).

m-(2-Vinyloxyethoxy)styrene. This styrene derivative was

synthesized on a 0.25 mole scale by the method used for o-

(2-vinyloxyethoxy)styrene. Fractional distillation under

vacuum through a spinning band column gave 17.7 g. (38%) of


~




73


a colorless liquid; b.p.: 73-7740c/0. 10mmI1g.

The NMR spectrum (CC14) of the compound gave absorp-

tions at 67.26-6.56 multiplee, 5H, aromatic H & PhCH=),

6.43 (quartet, 1H, OCH=, JaBcis = 7.2 Hz, J trans = 13.8 Hz),

5.63 & 5.15 (AB quartet, 2H, =CH2, AB = 1.3 Hz, JAX = 17.4

Hz, JBX = 10.5 Hz) and 4.28-3.71 multiplee, 6H, OC=CH2 &

OCC2CH20).

P-(2-Vinyloxyethoxy)benzaldehyde. This benzaldehyde was

prepared on a 0.5 mole scale by the method used for o-(2-

vinyloxyethoxy)benzaldehyde. Vacuum distillation of the

crude product yielded 70.3 g. (73%) of the product; b.p.:

1060C/0.15mmHg. The liquid solidified on standing; m.p.:

40-410C.

The NMR spectrum (CC14) of the compound gave absorp-

tions at 69.75 (singlet, 1H), 7.77-6.82 multiplee, 411),

6.43 (quartet, 1H), and 4.31-3.86 multiplee, 6H).

p-(2-Vinyloxyethoxy)styrene. This compound was prepared on

a 0.25 mole scale by the method used for o-(2-vinyloxyethoxy)-

styrene, but was purified differently. After the work-up,

the crude solid residue was extracted with petroleum ether

(b.p.: 30-750C). Evaporation of the combined extracts to

dryness gave a white crystalline solid, m.p.: 50-550C.

The solid was passed through a column packed with silica gel

using benzene as the eluent. Recrystallization from petro-

leum ether (b.p.: 30-750C) gave 21.2 g. (46%) of the pure

product; m.p.: 64.5-65.50C.









The NMR spectrum (CC14) of the compound gave absorp-

tions at 67.35-6.60 multiplee, 5H, aromatic H & PhCH=), 6.46

(quartet, 1H, OCH=, J acis = 6.8 Hz, JaBtrans = 14.2 Hz),

5.55 & 5.07 (AB quartet, 2H, =CH2, AB = 1.3 Hz, JAX = 17.4

Hz, JBX = 10.6 Hz), and 4.35-3.84 multiplee, 6H, OC=CH &

OCH2CH2O).

Synthesis of o-, m-, and p-Vinylphenoxyethanols

2-(o-Vinylphenoxy)ethanol. 14.4 g. (0.076 mole) of o-(2-

vinyloxyethoxy)styrene, 45 ml. of acetone, and 5 ml. of 10%

hydrochloric acid were placed in a 200 ml. round bottom flask

equipped with a magnetic bar. After being stirred at ambient

temperature for 30 min., the reaction was neutralized with 20%

sodium carbonate solution. After removal of the acetone on

a rotary evaporator the aqueous mixture was extracted with 50

ml. portions of chloroform twice. The combined chloroform

solution was washed with 30 ml. of water and then dried over

anhydrous sodium sulfate. Evaporation of the solvent gave an

oily residue, which was distilled on a high vacuum line

(approx. 104 mmHg.) by means of short path molecular distil-

lation with heating jacket temperature reading 1500C, 9.8 g.

of a white solid were obtained; m.p.: 34-35 C. The yield

was 79%.

The infrared spectrum (neat) of the compound showed

absorption bands at 3400 (s,b), 3090 (m), 3050 (m), 2940 (s),

2890 (s), 1627 (s), 1600 (s), 1580 (m), 1486 (s), 1450 (s),

1420 (m), 1376 (m), 1315 (m), 1295 (s), 1265 (s), 1165 (m),

1135 (m), 1110 (s), 1080 (s), 1050 (s), 1000 (s), 910 (s),

and 750 (s) cm1.









The NMR spectrum (CDCl3) of the compound showed signals

at 67.45-6.63 multiplee, 5H, aromatic H & PhCH=), 5.65 &

5.18 (AB quartet, 2H, =CH2, JAB = 1.7 Hz, JAX = 17.6 Hz,

JB = 11.0 Hz), 4.05-3.71 multiplee, 4H, OCH2CH20), and
BX 2 2
3.05 (singlet, 1H, OH).

The ultraviolet spectrum (1,4-dioxane) of the compound

gave absorption bands a 251 nm (c = 11,400) and 300 nm (e =

4,080).

Anal. Calcd. for C10H1202: C, 73.15; H, 7.37. Found:

C, 73.02; H, 7.42.

2-(m-Vinylphenoxy)ethanol. This monomer was prepared in a

manner entirely analogous to that for the previous monomer

on a 0.068 mole scale. 9.1 g. (81%) of a colorless liquid

was obtained by molecular distillation on a high vacuum

line (approx. 10- mmHg.) with heating jacket reading 1700C.

The infrared spectrum (neat) of the compound showed

absorptions at 3400 (s,b), 3100 (m), 3080 (m), 3020 (m),

2940 (s), 2880 (s), 1630 (m), 1600 (s), 1580 (s), 1435 (s),

1444 (s), 1415 (m), 1410 (m), 1387 (m), 1330 (m), 1310 (m),

1290 (s), 1260 (s), 1245 (s), 1172 (s), 1160 (s), 1080 (s),

1050 (s), 990 (s), 950 (s), 905 (s), 875 (m), 855 (m), 782
-I
(s), 735 (m), 715 (s), and 665 (s) cm1

The NMR spectrum (CDC13) of the compound showed signals

at 67.82-6.38 multiplee, 5H, aromatic H & PhCH=), 5.63 &

5.16 (AB quartet, 2H, =CH2, JAB = 1.3 Hz, JAX = 17.6 Hz,

JBX = 10.6 Hz), 4.08-3.73 multiplee, 4H, OCH2CH20), and
3.02 (singlet, 111, OH).









Anal. Calcd. for C10H1202: C, 73.15; H, 7.37. Found:

C, 72.92; H, 7.37.

2-(p-Vinylphenoxy)ethanol. Hydrolysis of 3.5 g. (0.018 mole)

of p-(2-vinyloxyethoxy)styrene gave a solid residue. Re-

crystallization from low-boiling petroleum ether yielded 2.5

g. (83%) of a white crystalline solid; m.p.: 65-660C.

The infrared spectrum (CC14) of the compound gave ab-

sorptions at 3630 (m), 3470 (m,b), 3100 (m), 3070 (w), 3050

(m), 3010 (m), 2490 (s), 2880 (m), 1630 (m), 1610 (s), 1580

(m), 1510 (s), 1455 (m), 1410 (m), 1370 (m), 1320 (m), 1300

(m), 1290 (m), 1245 (s), 1175 (s), 1115 (m), 1075 (s), 1040
-I
(s), 990 (m), 900 (s), and 830 (s) cm-1

The NMR spectrum (CDC13) of the compound showed signals

at 67.25-6.31 multiplee, 5H, aromatic H & PhCH=), 5.45 &

5.01 (AB quartet, 2H, =CH2, JAB = 1.2 Hz, JAX = 17.2 Hz,

JBX = 10.6 Hz), 4.06-3.70 multiplee, 4H, OCH2CH20), and
2.42 (singlet, 1H, OH).

Anal. Calcd. for C10H1202: C, 73.15; H, 7.37. Found:

C, 73.14; H, 7.38.

Synthesis of 2-(o-Vinlyphenoxy)ethyl Methacrylate and Acrylate

2-(o-Vinylphenoxy)ethyl methacrylate. 4.0 g. (0.024 mole)

of 2-(o-vinylphenoxy)ethanol, 3.6 g. of dry pyridine, and

200 ml. of anhydrous ethyl ether were placed in a 500 ml.

three-necked round bottom flask, which had been equipped with

an addition funnel, a mechanical stirrer, a gas inlet, and

a condenser protected by a drying tube. A slow flow of









nitrogen was maintained through the reaction. A solution

of 5.0 g. (0.048 mole) of methacrylyl chloride in 25 ml.

of anhydrous ether was added dropwise with constant stirring.

The reaction mixture was stirred continuously overnight.

At the end of the reaction, 50 ml. of water was added

to the reaction mixture. The ethereal solution was washed

with 50 ml. portions of 20% sodium carbonate solution three

times and with de-ionized water twice, and then dried over

anhydrous magnesium sulfate. Evaporation of the ether on a

rotary evaporator gave an oily residue, which contained an

impurity as indicated by spectral and TLC analyses. The

residual oil was passed through a column packed with silica

gel using benzene as the eluent. Distillation of the chro-

matograph purified product on a high vacuum line gave 1.6 g.

(29%) of a colorless liquid with a heating jacket tempera-

ture reading 1800C.

The infrared spectrum (neat) of the compound gave

absorption bands at 3080 (m), 3040 (m), 3030 (m), 2990 (s),

2970 (s), 2930 (s), 2890 (m), 1785 (w), 1720 (s), 1640 (s),

1630 (s), 1600 (s), 1580 (m), 1490 (s), 1450 (s), 1410 (s),

1380 (m), 1345 (w), 1320 (s), 1295 (s), 1245 (s), 1170 (s),

1110 (s), 1050 (s), 1000 (s), 940 (s), 930 (s), 910 (s),

815 (m), and 750 (s) cm-1.

The NMR spectrum (CDC13) of the compound showed signals

at 67.55-6.75 multiplee, 5H, aromatic H & PhCH=), 6.15-5.13

multiplee, 4H, =CH2 & PhC=CH2), 4.60-4.10 multiplee, 4H,

OCH2CH2O). and 2.0-1.90 multiplee, 31, CH3).








The ultraviolet spectrum (THF) of the compound gave

absorption maxima at 250 nm (E = 13,900) and 300 nm (e =

4,200).

Anal. Calcd. for C14H1603: C, 72.39; H, 6.94. Found:

C, 72.19; H, 7.12.

2-(o-Vinlyphenoxy)ethyl acrylate. The acrylate was prepared

by the procedure described above for the methacrylate except

that the chromatographic purification was not required. The

reaction was carried out on a 0.023 mole scale. Distillation

of the crude product on a high vacuum line gave 1.1 g. (22%)

of a colorless liquid with heating jacket temperature read-

ing 1800C.

The infrared spectrum (neat) of the compound gave

absorDtion bands at 3080 (m), 3040 (m), 2960 (m), 2940 (m),

2885 (m), 1725 (s), 1625 (s), 1600 (s), 1580 (m), 1485 (s),

1450 (s), 1410 (s), 1290 (s), 1270 (s), 1240 (s), 1185 (s),

1110 (s), 1060 (s), 985 (s), 940 (s), 910 (s), 845 (w),
-!
810 (s), 750 (s) and 705 (m) cm-1

The NMR spectrum (CDC13) of the compound showed signals

at 67.55-6.75 multiplee, 5H, aromatic H & PhCH=), 6.65-5.15

multiplee, 5H, CH=CH2 & =CH2), 4.62-4.11 multiplee, 4H,

OCH2 CH20).

Anal. Calcd. for C13H1403: C, 71.54; H, 6.47. Found:

C, 71.37; H, 6.65.

Polymerization Studies
Anionic Polymerization of (2-Vinyloxyethoxy)stvrenes

General procedures for the monomer and solvent purifi-









cation as well as the initiator preparation are described

as follows.

Monomer purification. The previously prepared liquid

monomer was dried over calcium hydride overnight and then

redistilled before use; the solid, recrystallized monomer

was dried in a desiccator, which contained phosphorus pent-

oxide, for one week. The purity of the monomer was checked

by spectral and chromatographic analyses.

Solvent purification. Tetrahydrofuran (THF) was pre-dried
o
over 5 A molecular sieves and then redistilled from calcium

hydride or lithium aluminum hydride. To the freshly redis-

tilled THF in a 1000 ml. round bottom flask were added a

small amount of potassium and sodium metal in a rough ratio

of two to one and a catalytic amount of benzophenone. The
-4
flask was degassed on a high vacuum line (10 mmHg.) until

the deep blue-purple color of the benzophenone ketyl solu-

tion persisted.

Initiator preparation. A 100 ml. Schlenk-type vessel equipped

with a magnetic bar was thoroughly evacuated and flamed on

a high vacuum line. After 50 ml. of the THF had been con-

densed into the flask, it was released from the vacuum line

by charging dry nitrogen or helium through the side-tube and

sealed with a rubber septum. 1.5 g of resublimed naphthalene

and 0.5 g. of sodium metal were quickly added when the vessel

was temporarily opened and maintained under an inert atmo-

sphere. The reaction mixture turned dark green gradually and









was stirred at ambient temperature for two hours. The

concentraiton of the naphthalide in the solution was deter-

mined by titration against standard 0.100 N. hydrochloric

acid using a mixture of methanol and de-ionized water as the

solvent and phenolphthalein as the indicator.

Anionic polymerization of p-(2-vinyloxyethoxy)styrene. A

100 ml. Schlenk-type vessel equipped with a magnetic bar was

evacuated and flamed on a high vacuum line, followed by

transferring into it 35 ml. of THF. The flask was released

from the vacuum line by charging dry nitrogen through the

side-tube, and was immediately sealed with a rubber septum.

8.0 g. (0.042 mole) of the monomer were added through the

septum by using a dry syringe, and the solution was well

stirred. After the solution had been cooled to -780C in a

dry ice-isopropanol bath, 2 ml. of the initiator solution

(0.185 mmole/ml.) was injected into the flask in one shot,

and the solution turned orange-red immediately, indicating

the formation of the "living" styryl anion. The solution

became very viscous within a few minutes and stirring was

difficult. The solution was maintained at the low tempera-

ture for one hour. After the end of the reaction, the solu-

tion still maintained its characteristic color, and was

terminated by adding 2 ml. of methanol. Precipitation of

the polymer solution from a bulky amount of methanol gave a

white powdery solid, which was filtered, washed, and dried

in vacuo at ambient temperature overnight. The yield was









7.5 g. (94% conversion). The intrinsic viscosity of the

polymer in benzene at 25 C was 0.438 dl/g., and the melting

point of the polymer was 80-850C. The polymer had a number-

average molecular weight (M ) in toluene of 2.45 x 10 which
n
is equivalent to a degree of polymerization (DP) of 1290, and

a molecular weight distribution (M /Mn) value of 1.16.

The NMR spectrum (CC1l) of the polymer showed signals

at 67.15-5.85 multiplee, 5H), 4.2-3.0 multiplee, 6H), and

2.9-0.8 multiplee, 3H).

The infrared spectrum (KBr) of the polymer gave absorp-

tion bands at 3120 (w), 3070 (m), 3030 (m), 2930 (s), 2870

(m), 1640 (s), 1620 (s), 1595 (s), 1585 (m), 1490 (s), 1450

(s), 1360 (m), 1320 (s), 1290 (m), 1240 (s), 1200 (s), 1110

(s), 1090 (s), 1050 (s), 1010 (m), 985 (s), 965(s), 930 (s),

810 (s), and 745 (s) cm1.

The ultraviolet spectrum (1,4-dioxane) of the polymer

showed absorption maxima at 273.5 nm (E = 2,070) and 279.5

nm (c = 1,830).

Anal. Calcd. for (C12H1402)n: C, 75.76; H, 7.42.

Found: C, 75.67; H, 7.48.

Anionic polymerization of m-(2-vinyloxyethoxy)styrene. The

polymerization of the m-isomer was carried out twice by the

same method as previously described for the o-isomer; only

the second run is briefly described as follows (see Table 1,

page 24, for the data of the first run). Charged to a

Schlenk-type flask were 60 ml. of THF, 14.9 g. (0.078 mole)

of the monomer, and 4 ml. of the initiator solution (0.190









mmole/ml.). The orange-red solution was maintained at -450C

for one hour and then terminated with 2 ml. of methanol.

Precipitation of the polymer solution from methanol gave

14.9 g. (100% conversion) of a white soft gum; Tm: 35-400C.

The intrinsic viscosity of the polymer in benzene at 250C

was 0.619 dl/g. The polymer had a number-average molecular

weight (4 ) in toluene of 1.63 x 105, which is equivalent to

a degree of polymerization (DP) of 860, and a molecular

weight distribution (M w/ ) value of 1.97.

The infrared spectrum (CC14) of the polymer gave absorp-

tion bands at 3130 (w), 3050 (w), 2930 (s), 2890 (m), 1655

(m), 1640 (m), 1610 (s), 1600 (s), 1535 (s), 1485 (s), 1450

(s), 1365 (m), 1320 (s), 1260 (s), 1203 (s), 1160 (s), 1105

(m), 1080 (m), 1055 (m), 985 (s), 965 (m), 945 (m), 855 (m),

and 700 (s) cm1.

The ultraviolet spectrum (1,4-dioxane) of the polymer

showed absorption maxima a 273.5 nm (e = 1,940) and 279.5

nm (E = 1,780).

Anal. Calcd. for (C12H14s )n: C, 75.76; H, 7.42.

Found: C, 75.95; H, 7.34.

Anionic Polymerization of p-(2-vinyloxyethoxy)styrene. The

polymerization was run twice by the procedure previously

described; only the second run (see Table 1, page 24 for the

first run) is described here. To a solution of 2.8 g. (0.015

mole) of the monomer in 30 ml. of refined THF was added 3 ml.

of the initiator solution (0.130 mmole/ml.) after the reac-

ton flask had been cooled to -450C. After being stirred at









the low temperature for one hour, the dark red solution was

terminated by adding 2 ml. of methanol. 2.6 g (92% conver-

sion) of a white powdery solid were obtained by precipita-

tion of the polymer solution from low-boiling petroleum

ether. Unlike the polymeric o- and m-isomers, the polymer

obtained from the p-isomer became partially insoluble with-

in a few days. To 2.5 g. of the partially insoluble polymer

was added 30 ml. of benzene, and the mixture was stirred at

ambient temperature for 6 hours. Filtration of the mixture

through a coarse sintered-glass funnel gave a clear solution.

Reprecipitation of the benzene solution from petroleum ether

gave 1.0 g (40% recovery) of a soluble polymer, which did

not change its solubility characteristics over a long period

of time. The intrinsic viscosity of the soluble portion of

the polymer in benzene at 250C was 0.155 dl/g. and the

melting point of the polymer was 45-500C. The polymer had

a number-average molecular weight (Mn) in toluene of 9.19 x

10 which is equivalent to a degree of polymerization (DP)

of 480, and a molecular weight distribution ( /Mn) value

of 1.11.

The infrared spectrum (KBr) of the polymer gave absorp-

tion bands at 3130 (w), 3040 (m), 2930 (s), 2890 (s), 1660

(m), 1640 (s), 1610 (s), 1587 (m), 1510 (s), 1450 (s), 1425

(w), 1370 (m), 1325 (s), 1302 (m), 1247 (s), 1200 (s), 1175

(s), 1105 (s), 1070 (s), 1050 (s), 1012 (m), 980 (s), 927 (m),

820 (s), and 700 (w) cm-1.
820 (s), and 700 (w) cm








The NMR spectrum (CC1,) of the polymer showed signals

at 66.8-6.1 multiplee, 5H), 4.2-3.7 multiplee, 6H), and

2.2-0.6 multiplee, 3H).

The ultraviolet spectrum (1,4-dioxane) of the polymer

showed absorption maxima at 277.5 nm (c = 1,610) and 285 nm

(E = 1,350).

Anal. Calcd. for (C12H1402)n: C, 75.76; H, 7.42.

Found: C, 75.34; H, 7.18.

Radical Polymerization of the o-, m-, and p-(2-Vinyloxyethoxy)-
styrenes

Radical polymerization of o-(2-vinyloxyethoxy)styrene. Charged

to a polymer tube were 0.566 g. (2.98 mmole) of the monomer,

3.8 ml. of benzene, and 5.2 mg. of azobisisobutyronitrile

(AIBN). The polymer tube was attached to a high vacuum line,

frozen in a dry ice-isopropanol bath, and then evacuated.

The solution was subjected to three cycles of freeze-thaw

method, and the tube was then sealed under vacuum. The sealed

tube containing the monomer, solvent, and initiator was

placed in an oil bath set at 700C, and was heated at this

temperature for 24 hours. At the end of the polymerization,

the tube was removed from the heating bath and opened. A

minute amount of gel formed on the tube wall was observed.

The polymer solution was poured into a large amount of

petroleum ether (b.p. 30-750C) to give a white precipitate,

which was filtered, washed, and dried in a vacuum pistol at

ambient temperature. The yield of the white powdery polymer

was 0.245 g. (43.3% conversion). The intrinsic viscosity of

the polymer in benzene at 300C was 0.332 dl/g.









The infrared spectrum of the polymer was identical to

that of the polymer obtained by anionic initiation of the

same monomer; so were the melting point and solubility

characteristics.

Radical polymerization of m-(2-vinyloxyethoxy)styrene. The

m-isomer was polymerized by the same procedure described

above for the o-isomer. Charged to a polymer tube were

0.361 g. (1.90 mmole) of the monomer, 2.4 ml. of benzene,

and 3.7 mg. of AIBN. The degassed and sealed tube was heated

in a 700C bath for 24 hours. Precipatation of the polymer

solution from excess low-boiling petroleum ether gave 0.206

g. (57% conversion) of a white soft gum, which had exactly

the same appearance as the one previously obtained by anionic

polymerization. The intrinsic viscosity of the polymer in

benzene at 300C was 0.224 dl/g. The other physical proper-

ties and infrared spectrum of the polymer were identical to

those of the anionic-initiated polymer.

Radical polymerization of p-(2-vinyloxyethoxy)styrene. The

p-isomer was polymerized under the same reaction conditions

as those previously described for the o- and m-isomers.

Charged to a polymer tube were 0.327 g (1.72 mmole) of the

monomer, 2.2 ml. of benzene, and 3.4 mg. of AIBN. After

being heated at 700C for 24 hours, the polymer solution was

precipitated from petroleum ether to give a white powdery

solid. The yield was 0.126 g (38.5% conversion). It should

be noted that this radically initiated polymer did not show

any change in solubility over a long period of time. The









intrinsic viscosity of the polymer in benzene at 300C was

0.222 di/g. The other physical properties and infrared

spectrum of the polymer were identical to those of the

anionically initiated polymer.

Post-Cationic Polymerization of Poly-(2-vinyloxyethoxy)-
styrenes

The polymer samples were dried under vacuum before use.

Toluene was selected as the solvent, which was dried over

calcium hydride and distilled before use.

Post-cationic polymerization of poly[o-(2--vinyloxyethoxy)-

styrene]. A 100 ml. Schlenk-type vessel was evacuated and

flamed on a vacuum line. After cooling, 0.57 g. of the

polymer and 50 ml. of toluene were added, and the vessel

was flushed with dry nitrogen and capped with a rubber sep-

tum. The solution was cooled in a dry ice-isopropanol bath,

and then 3 ml. of boron trifluoride gas was added by

syringe. The reaction mixture was maintained at the low

temperature for 2 hours. At the end of the period, the

reaction contents were poured into an excess amount of meth-

anol, centrifuged, washed, and dried in vacuum. The yield

of a yellow powdery solid was 0.50 g. (88% conversion). The

polymer decomposed slightly at about 3000C, and it was in-

soluble in all solvents tried.

The infrared spectrum (KBr and nujol) of the polymer

showed absorption bands at 3070 (m), 3035 (m), 2930 (s),

2880 (s), 1600 (m), 1587(m), 1485 (s), 1445 (s), 1360 (m),

1290 (m), 1230 (s), 1115 (s), 1050 (s), 920 (m), 735 (w),

and 740 (s) cm-1









Post-cationic polymerization of poly[m-(2-vinyloxyethoxy)-

styrene]. Charged to a 100 ml. Schlenk-type vessel were

0.48 g. of the polymer and 50 ml. of toluene. After being

cooled to -78C, 2.5 ml. of boron trifluoride gas was intro-

duced into the solution via a syringe, and the solution was

maintained at that temperature for 2 hours. Precipitation

from methanol gave 0.45 g (94% conversion) of a yellow pow-

dery solid. The polymer was insoluble in all solvents tested,

and it was slightly discolored at 3000C.

The infrared spectrum (KBr and nujol) of the polymer

gave absorption bands at 3060 (m), 3030 (m), 2920 (s),

2880 (s), 1600 (s), 1585 (s), 1480 (s), 1440 (s), 1350 (m),

1256 (s), 1100 (s), 1060 (s), 950 (m), 860 (m), 777 (s),

and 697 (s) cm1.

Post-cationic polymerization of poly[p-(2-vinyloxyethoxy)-

styrene]. Charged to a 100 ml. Schlenk-type vessel were

0.11 g. of the polymer and 10 ml. of toluene. 0.8 ml. of

boron trifluoride gas was injected into the bottle after the

solution had been cooled to -780C. The reaction was con-

tinued for 2 hours at the low temperature. Precipitation by

methanol addition gave 0.091 g. (83% conversion) of a yellow

solid, which slightly decomposed at 3000C. The product was

insoluble in all solvents tried.

The infrared spectrum (KBr and nujol) of the polymer

showed absorptions at 3030 (w), 2920 (s), 2880 (s), 1610 (s),

1580 (m), 1500 (s), 1450 (s), 1370 (m), 1295 (m), 1240 (s),

1185 (m), 1110 (m), 1070 (s), 1040 (s), 900 (s), and 820 (s)
-1
cm









Polyvinylphenoxyethanols from Hydrolysis of Poly-(2-vinyloxy-
ethoxy)styrene

Poly[2-(o-vinylphenoxy)ethanol] from hydrolysis of poly-[o-

(2-vinyloxyethoxy)styrene]. 1.91 g. of the polymer, 45 ml.

of acetone, and 5 ml. of 10% hydrochloric acid were mixed

and stirred in a 100 ml. round bottom flask. After being

stirred at ambient temperature for 24 hours, the clear

polymer solution was neutralized with 1 N. methanolic ammonia.

The neutralized solution was poured into 500 ml. of stirring

de-ionized water, filtered, washed, and dried in vacuum at

6000C. The product was a white powdery solid and the yield

was 1.59 g. (97% conversion). The polymer had an intrinsic

viscosity of 0.485 dl/g. in dimethylformamide (DMF) or 0.267

dl/g. in tetrahydrofuran (THF). The melting point of the

polymer was around 170-1800C.

The infrared spectrum (KBr) of the polymer gave absorp-

tion bands at 3570 (s), 3410 (b, s), 3060 (w), 3030 (w),

2930 (s), 2870 (s), 1597 (m), 1583 (m), 1490 (s), 1448 (s),

1370 (w), 1290 (m), 1240 (s), 1160 (w), 1105 (s), 1075 (s),

1034 (s), 915 (m), 890 (m), 800 (w), and 745 (s) cm-1

The NMR spectrum (CDCl3) of the polymer showed signals

at 67.3-6.2 multiplee, 4H), 4.1-3.0 multiplee, 4H), and

3.0-0.8 multiplee, 4H).

The ultraviolet spectrum (1,4-dioxane) of the polymer

showed absorption maxima at 274 nm (c = 1,930) and 280 nm

(e = 1,700).

Anal. Calcd. for (C10H 202)n: C, 73.14; H, 7.37. Found:

C, 72.94; H, 7.53.









Poly[2-(m-vinylphenoxy)ethanol] from hydrolysis of poly[m-

(2-vinyloxyethoxy)styrene]. 1.82 g. of the polymer was

hydrolyzed by the same method as previously described for

the polymeric o-isomer. Precipitation of the neutralized

polymer solution from de-ionized water gave 1.51 g (96%

conversion) of a white powdery solid. The melting point of

the polymer was around 100-1100C and the intrinsic viscosity

of the polymer in DMF was 1.27 dl/g.

The infrared spectrum (KBr) of the polymer gave absorp-

tion bands at 3360 (b, s) 3030 (w), 2920 (s), 2870 (s), 1600

(s), 1580 (s), 1480 (s), 1440 (s), 1370 (w), 1312 (m), 1250

(s), 1153 (s), 1070 (s), 1040 (s), 995 (w), 950 (m), 890 (m),

774 (s), and 693 (s) cm-1.

The ultraviolet spectrum (1,4-dioxane) of the polymer

gave absorption maxima at 273 nm (c = 1,980) and 279.5 nm

(e = 1,830).

Anal. Calcd. for (C12H1002)n: C, 73.14; H, 7.37. Found:

C, 72.50; H, 7.23.

Poly[2-(p-vinylphenoxy)ethanol] from hydrolysis of poly[p-

(2-vinyloxyethoxy)styrene]. The hydrolysis of the polymer

was carried out by the same method as previously described

for the polymeric o- and m-isomers except on a much smaller

scale. 0.189 g. of the polymer was hydrolyzed to give 0.152

g. (93% conversion) of a white solid. The polymer product

had an intrinsic viscosity in DMF of 0.219 dl/g. and a melt-

ing point of 155-1650C.









The infrared spectrum (KBr) of the polymer showed

absorptions at 3390 (b, s), 3040 (w), 2930 (s), 2880 (m),

1610 (s), 1585 (m), 1510 (s), 1454 (m), 1425 (w), 1373 (m),

1304 (m), 1245 (s), 1179 (s), 1110 (w), 1080 (s), 1050 (s),

915 (s), and 827 (s) cm1.

Anal. Calcd. for (C10H1202)n: C, 73.14; H, 7.37. Found:

C, 71.40; H, 6.87.

Radical Polymerization of o-, m-, and p-Vinylphenoxyethanols

For these experiments, benzene and tetrahydrofuran (THF)

were selected as the solvents and distilled before use.

Radical polymerization of 2-(o-vinylphenoxy)ethanol. Charged

to a polymer tube were 1.40 g. (8.53 mmole) of the monomer,

5.0 ml. of benzene, and 11.3 mg. of AIBN. The solution was

degassed on a vacuum line, subjected to three cycles of the

free-thaw method, and then sealed under vacuum. The sealed

tube was placed in an oil bath set at 700C, and heated at

this temperature for 72 hours. During the heating period,

a white precipitate gradually formed, indicating the polymer

was not soluble in the solvent. At the end of the polymer-

ization the precipitate was filtered, washed with low-boiling

petroleum ether, and dried in vacuum at 60 C. Dissolution

of the dried polymer in 20 ml. of THF followed by reprecip-

itation from 400 ml. of petroleum ether gave 1.21 g. (86%

conversion) of a white powdery solid. The intrinsic viscosity

of the polymer was 0.374 dl/g. in DMF or 0.196 dl/g. in THF.

The melting point, solubility characteristics, and infrared




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