Beruflich Dokumente
Kultur Dokumente
Mortsel-Antwerp (Belgium)
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.
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.
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.
47
G. VANPAESSCHEN,
R. JANSSEN, and R. HART
-CH,- CH-
I
OCO- CH =CH-- C,H
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
48
Cyclopolymerization of Vinyl trans-Cinnamate
- Lactone
Monomer
Solvent con,.. Init.*) Temp. Time
"C. hrs.
%
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
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)
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)
50
Cyclopolymerization of Vinyl trans-Cinnamate
OCA OC,H,
(X)
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
51
R. JANSSEN, and R. HART
G. VANPAESSCHEN,
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.
Acknowledgement
lS) H. M. BUCKWALTER
and E. C. WAGNER,J. Amer. chern. SOC.52 (1930) 5241.
52