1070-4272/05/7802-0311 C 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 2, 2005, pp. 311!314. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005,
Original Russian Text Copyright + 2005 by K. Guliev, Ponomareva, A. Guliev.
AND POLYMERIC MATERIALS
Copolymerization of 2-Chloro-Substituted p-Cyclopropylstyrenes
with Styrene and Properties of the Resulting Copolymers
K. G. Guliev, G. Z. Ponomareva, and A. M. Guliev
Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgait, Azerbaijan
Received July 14, 2004
Abstract-2,2-Dichloro- and 2-chloro-1-(p-vinylphenyl)cyclopropanes were prepared and brought into co-
polymerization with styrene. The effect of substituents on the reactivity of the monomers was examined.
The physicomechanical properties of the copolymers were studied.
One of the ways to improve the physicomechani-
cal, thermal, and optical properties and enhance the
flame resistance of polystyrene plastics is copolymer-
ization of styrene with other monomers. In so doing,
it is possible to vary the properties of the copolymers
in a wide range.
The copolymerization of styrene with substituted
styrenes has been studied extensively .
In this study, we prepared 2,2-dichloro- and 2-chlo-
ro-1-(p-vinylphenyl)cyclopropanes (I, II, respectively)
and performed their copolymerization with styrene in
the bulk and in solution; we also examined the effect
of the chlorinated substituents on the reactivity of the
monomers and on the properties of the resulting co-
polymers. We found that styrene smoothly copolymer-
izes with the monomers synthesized, without opening
of the cyclopropane ring; the resulting copolymers are
The copolymerization under the conditions of our
experiments occurred through opening of the double
bond, yielding macromolecules with pendant phenyl
groups (unsubstituted and those bearing chlorinated
cyclopropane fragments). This is suggested by the
spectra of the copolymers. The ratio of the monomeric
units (I or II to styrene) in the copolymer was esti-
mated from the chlorine content determined by ele-
The IR spectra of both the starting monomers and
copolymers thereof contain characteristic bands be-
longing to vibrations of the C3Cl bond (675 cm
and cyclopropane ring (103031040 cm
). The spectra
of the copolymers also contain well-defined bands at
1450, 1500, 1585, and 1605 cm
belonging to vibra-
tions of the benzene ring. Strong bands at 1213 and
and bands at 1110 and 1013 cm
characteristic of 1,4-disubstituted benzenes and belong
to the in-plane bending modes of the four hydrogen
atoms of the benzene ring.
Changes in the intensities of the bands belonging
to the main functional groups of I and II suggest
changes in the composition of the monomeric units.
The IR data allow us to ascribe the following struc-
ture to the copolymers:
where X = 2Cl (I), Cl (II).
For this pair of monomers, we calculated the co-
polymerization constants and the Alfrey3Price param-
eeters Q and e . To evaluate the distribution of
units in the macromolecular chain, we calculated the
microstructural parameters L
, and R . The
results are listed in Table 1.
Table 1 shows that, at any ratio of the starting
monomers, the copolymer is always enriched in units
of mono- or gem-dichloro-substituted cyclopropyl-
styrenes, which is due to the higher reactivity of these
monomers, caused by the presence of the substituted
The chlorine atoms, which are present in I and II as
substituents in the cyclopropane ring and are separated
from the reaction center by the phenyl ring and a cy-