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From the Chemical Research Department, Gevaert Photo-Producten N.V.

Mortsel-Antwerp (Belgium)

Cyclopolymerization of Vinyl trans- Cinnamate*


By G. VANPAESSCAEN,
R. JANSSEN and R. HAHT

(Eingegangen am 20. November 1959)

SUMMARY:
Vinyl trans-cinnamate, an unsymmetrical divinyl monomer, has been synthesized, and
polymerized t o linear, soluble polymers.
It was found by infrared and chemical analysis that these polymers are quite different
from polyvinyl cinnamates synthesized through esterification of polyvinyl alcohol by cinn-
amoyl chloride.
The polymers prepared by polymerization of the monomer are characterized by the
presence of y-lactone rings resulting from a cyclopolymerization mechanism.

ZUSAMMENFASSUNG:
Vinyl-trans-cinnamat, ein asymmetrisches Divinylmonomeres, wurde synthetisiert
und aus ihm ein lineares losliches Polymeres hergestellt.
Mit Hilfe von Infrarotspektren sowie a d chemischem Wege konnte gezeigt werden,
da13 diese Polymeren sich von einem Polyvinylcinnamat, das durch Veresterung von
Polyvinylalkohol mit Zimtsaurechlorid erhalten wurde, wesentlich unterscheiden.
Die Polymeren, die durch Polymerisation des Monomern erhalten wurden, sind durch
die Anwesenheit von y-Lacton-Ringen, die infolge eines Cyclopolymerisationsmechanis-
mus entstanden, gekennzeichnet.

It is known from recent publications by several authors1-') that sym-


metrical divinyl and diallyl monomers whose double bonds are in a 1-5
or a 1-6 position polymerize t o linear, saturated and soluble polymers.
*) Communication presented a t the IUPAC-Symposium on Macromolecules, Wiesbaden,
October 1959.
I) G. B. BUTLERand F. L. INGLEY, J. Amer. chem. SOC.73 (1951) 895.
2, G. B. BUTLERand R. J. ANGELO,J. Amer. chem. SOC.79 (1957) 3128.
3, G. B. BUTLER,A. CRAWSHAW, and W. L. MILLER, J. Amer. chem. SOC.80 (1958) 3615.
4, A. CRAWSHAWand G. B. BUTLER, J. Amer. chem. Soc. 80 (1958) 5464.
5, C. S. MARVEL and R. D. VEST,J. Amer. chem. SOC. 79 (1957) 5771; 81 (1959) 984.
6 , C. S. MARVELand J. K. STILLE,J. Amer. chem. Soc. 80 (1958) 1740.
') J. F. JONES,J. Polymer Sci. 33 (1958) 1, 15, 513.

46
Cyclopolymerization of Vinyl trans-Cinnamate

I ~ u T L E K ~ ,has
~ ) shown that the growth of such polymers procccds
through an alternating intramolecular-intermolecular chain propagation
resulting in the formation of cyclic structures.

R* + CH,=CH CH=CH, -+

c H, ,CH,
R-CH,-CH* CH + R-CH,-CH ‘CH.

JONES7) proposed for this growth mechanism the name of cyclopoly-


merization.
We have now observed that vinyl trans-cinnamate (I),which is char-
acterized by the presence of two different kinds of double bonds shows a
similar type of polymerization.

CH2=CH-OCO-CH=CH-C6Hj (1)

To our knowledge vinyl cinnamate has not yet been described in the
literature. Only a patent E, mentions, without further details, that this
monomer polymerizes t o completely insoluble polymers.
I n this paper we compare the structure and properties of polyvinyl
cinnamates synthesized respectively by polymerization of the monomer
and by esterification of polyvinyl alcohol.

Results and Discussion

Vinyl cinnamate, polymerized in bulk in the presence of benzoyl per-


oxide or azo-bis-isobutyronitrile, yields insoluble polymers. On the
contrary, if the monomer is polymerized in dilute solution (concentration
less than 30 yo)polymers are obtained which are soluble in several or-
ganic solvents, if the conversion is not too high (up t o about 50 yo).Their
intrinsic viscosity is situated between 0.2 and 0.7 dl. 8-l (in chloroform,
at 25°C.).
The solubility of these polyvinyl cinnamates (polymer M) can be ex-
plained by a linear structure. The absence of cross-linking may be due
either t o a lack of reactivity of the cinnamic double bond either t o a
cyclopolymerization. I n the first case the polymers should have practi-
cally the same structure as the esterification products of polyvinyl alco-
hol by cinnamic acid (polymer P) (11).
*) I,. M. MINSK (Eastman Co.), USP. 2,725,372 (prior. 20. 1 . 1951).

47
G. VANPAESSCHEN,
R. JANSSEN, and R. HART

-CH,- CH-
I
OCO- CH =CH-- C,H

In the other case, if the growth of the polymer proceeds through a


cyclopolymerization, the polymers should be characterized by the pre-
sence of y-lactone rings (111).

0-CO 0-c 0
I
R. + H,C=CH CH --+ R-CH,-CH* CH

6
C,H,
//
CH
C,HS

0 - - CO
-, R-CH,-CH CH.
‘Cf;
C,H,

The infrared spectra of the polymers M and P show that these are
indeed different (Fig. 1).

1001 ,

-100

Fig. 1 . Infrared spectra.


A. Polyvinyl cinnamate prepared by esterification of polyvinyl alcohol (polymer P)
B. Polyvinyl cinnamate obtained by polymerization of the monomer (polymer M)

48
Cyclopolymerization of Vinyl trans-Cinnamate

The absorption bands at 5.81 p (C=O), 6.08 p (C=C), 7.60-8.00


and 8 . 5 2 ~(C-0) and a t 10.2Op (CH=CH), characteristic of the
-CH=CH-COOR group are very strong in the spectra of polymer P,
while they are weak in the spectra of polymer M. This polymer, however,
shows strong bands a t 5.62 p ( C = O ) and 8.62 p (C-0), which are to
be ascribed to y-lactone rings ; indeed y-butyrolactone exhibits strong
absorption bands a t 5.62 and 8.59 p.
Considering these data and also the weakening of the bands corre-
sponding to the -CH=CH- group (6.08 and 10.20 p) it may be concluded
that the polymerization of vinyl cinnamate proceeds chiefly according t o
a cyclopolymerization mechanism. It should be noted however that poly-
mer M also contains some unsaturated ester groups of type 11. The
number of residual double bonds has been estimated by infrared spectro-
graphy. For this purpose a reference curve has been established using
solutions of polymer P (100 % structure 11) in chloroform and plotting
the extinction a t 6.08 p as a function of the concentration. Values ob-
tained for polymers M indicate a double bond content of about 15 to
20 %, whatever the polymerization conditions ; this corresponds to a
y-lactone content of 80 t o 85 yo (Table I).

- Lactone
Monomer
Solvent con,.. Init.*) Temp. Time
"C. hrs.
%

Benzene ....... 10 AIBN 60 45 26 85


Benzene ....... 25 AIBN 60 4 22 82
Dioxane ....... 25 BP 100 15 40 83
- 100 AIBN 60 4 6 77

0-CO
OH-
H' '
C,H, CO-CH=CH-CeH,

[
- -CH,-CH-CH-CH-
AH &H5 I
- -CH2-CH-
COOH],[ OH 1.
-
+ n C,H,-CH=CH-COOH

49
R. JANSSEN,
G. VANPAESSCHEN, and R. HART

The infrared analysis has been confirmed by chemical functional analy-


sis: hydrolysis of the polymer and determination of the liberated
cinnamic acid by bromometry.
According to this method the first polymer of Table I has a lactone
content of 86.3 yo in good agreement with the value found by infrared
spectroscopy. The composition of polyvinyl cinnamate (polymer M)
corresponds thus to structure IV where m/n 5 .
Concerning the mechanism of the polymerization of vinyl cinnamate,
one has to keep in mind that the presence of two different double bonds
complicates somewhat the exact picture of the growth mechanism. If
one takes into account the reactivity of the cinnamic double bondgJo),
the addition of a cinnamic group to a growing chain is not a priori ex-
cluded :
+ CH=CH
Re
I
‘0 GH5
A-cH-cH,
4

to
R-CH-CH-
‘EH5

O-CH=CH,

(V)
or
R* + CH=CH R-CH-CHF
C,H,
I LOOCH-CH, --j
d8H5 LOOCH=CH,

(VI)

Radicals such as V and VI could also undergo subsequent cyclizations.

CH CH
!E lE

V +
/T
R-CH CH, or
CH
R - 6 ‘CH-CHp
I !
CO CH* CO-b
‘0’
(VII) (VIII)

,c$$
VI+ R-CH-CH CH.
I I
C,H5 20-0
(IX)

O) C. S. MARVELand G. H. MCGAIN,J. h e r . chem. SOC. 75 (1953) 3272.


lo)C. S. MARVEL, G. H. MCGAIN,
M. PASSER, W. K. TAFT, and B. G. LABBE,Ind. Engng.
Chem. 45 (1953) 2311.

50
Cyclopolymerization of Vinyl trans-Cinnamate

eImportant contributions of structures such as V, VI and V I I in p l y -


m 0 r M do not seem very likely owing t o the absence of strong infrared
a sorption bands corresponding t o -CH=CH, groups or t o unconjugated
C=O groups in linear esters and 8-lactone rings. Structure V I I I however,
which is similar t o the above proposed structure 111, and structure I X ,
another type of y-lactone, are not excluded b y infrared evidence.
I n order t o determine the probability of t h e addition of a cinnamic
double bond t o a growing chain, we wanted t o compare the cyclopoly-
merization of vinyl cinnamate t o the copolymerization of vinyl acetate
a n d ethyl cinnamate. The copolymers contained however practically no
vinyl acetate even when a large excess of t h e last was used. This be-
havior is similar t o t h e copolymerization of vinyl acetate a n d styrenell)
a n d results probably from t h e stabilization of t h e benzyl radicals (X)
which, owing t o their greater stability, are the more probable inter-
mediates.
Re + CH=CH 3 R-CH-CH*
I CO &H,
C O C,H,
I

OCA OC,H,
(X)

On the contrary, in t h e case of the polymerization of vinyl cinnamate


t h e intermediate radicals which are of the acrylate type (111) - a n d
perhaps also of type V I I I a n d I X - are less stabilized, allowing t h e
subsequent addition of vinyl ester groups.
From the evidence presented i t may be concluded t h a t t h e polymeri-
zation of vinyl cinnamate is undoubtly accompanied by t h e formation of
y-lactone rings; t h e exact mechanism of t h e different steps of t h e propa-
gation is however not established with certainty.

Experimental Part

Vinyl trans-cinnamate
Vinyl cinnamate was synthetized by acidolysis of vinyl acetate by trans-cinnamic acid
according to the classical synthesis of vinyl esters12). B. p.: 125OC./7 mm. nfj: 1.5852
Analysis: calculated for C,,H,,O,: C 75.86, H 5.75, 0 18.39
found : C 76.05, H 5.85, 0 18.16

11) T. ALFREY,Jr., J. J. BOHRER,and H. MARK,Copolymerization, Intersci. Publ. Inc.


New York 1952, p. 59.
12) D. SWERNand E. F. JORDAN, Jr. in Org. Syntheses 30 (1950) 106.

51
R. JANSSEN, and R. HART
G. VANPAESSCHEN,

Polyvinyl cinnamate (polymer M)


Vinyl cinnamate was polymerized in sealed tubes, under nitrogen. Polymers were iso-
lated and purified by dissolution in chloroform and precipitation in ether.

Polyvinyl cinnamate (polymer P)


Polymer P was prepared by reaction of polyvinyl alcohol with cinnamoyl chloride ac-
cording to the method of MINSK~).

Analysis: calculated: C 75.86, H 5.75, 0 18.39


found : C 75.53, H 5.59, 0 18.38

Infrared analysis
The spectra of Figure 1 were recorded on a PERKIN-ELMER Infracord using the KBr
technique. For the quantitative analysis of chloroform solutions the spectra were recorded
on a PERKIN-ELMER-Type 2 1 double-beam spectrophotometer.

Determination of uncyclized cinnamate groups


A suspension of 500 mg. polymer in 20 ml. NaOH 0.5 N is refluxed during 15 hrs., while
the polymer gradually dissolves. The solution is acidified with an equivalent quantity of
aqueous HCl and freeze-dried. The cinnamic acid is extracted with carbon tetrachloride
and titrated b r o m ~ m e t r i c a l l y ~ ~ ) .
Preliminary tests indicated that the polymer was completely hydrolyzed in the con-
ditions used.

Acknowledgement

We wish to thank Prof. Dr. A. VAN DORMAEL, Head of the Chemical


Research Department, for his kind interest in this work.

lS) H. M. BUCKWALTER
and E. C. WAGNER,J. Amer. chern. SOC.52 (1930) 5241.

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