Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 12, pp. 2114−2117.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © K.G. Guliev, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 12, pp. 1230−1233.
AND POLYMERIC MATERIALS
Copolymerization of p-(2,2-Dichlorocyclopropyl)styrene
with Methyl Methacrylate and Properties
of the Resulting Copolymers
K. G. Guliev
Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgait, Azerbaijan
Received April 5, 2011
Abstract—A copolymer based on p-(2,2-dichlorocyclopropyl)styrene and methyl methacrylate was prepared
by radical copolymerization. The copolymerization constants were determined, and the parameters of the Q–e
scheme were calculated.
Studies in the ﬁ eld of synthesis and properties of
polymers and copolymers containing reactive groups
are of indubitable interest, because thermal and
photochemical transformations of such reactive polymers
allow preparation of valuable polymeric materials
exhibiting high radiation sensitivity in combination with
high resolving power and plasma chemical resistance.
Such materials are used in microelectronics as resists for
the transfer of images onto semiconductor plates [1–5].
Despite ample experimental data on the development
of photosensitive polymers, accumulated by now,
search for new, more effective materials of this kind is
being continued. Strong effect on the photosensitivity of
polymers is exerted by the structure of their molecular
chain and by the presence of various functional groups
Polymers with regular arrangement of cyclopropane
groups in pendant chains or in the backbone were
prepared by polymerization and copolymerization of
cyclopropane-containing vinyl compounds, which show
much promise as reactive monomers [6–10].
This study deals with the copolymerization of p-(2,2-
dichlorocyclopropyl)styrene (DCCPS) with methyl
We synthesized soluble copolymers containing
highly reactive dichlorocyclopropyl groups capable
of thermal and photochemical transformations. These
groups impart high photosensitivity to the polymers,
allowing preparation of photoresist materials from them.
Our studies showed that DCCPS in the presence
of AIBN at 70°С copolymerizes with MMA both in
the bulk and in a benzene solution. The yield of the
polymeric products reaches 95%. An increase in the
content of DCCPS in the reaction mixture leads to an
increase in the overall reaction rate. A dilatometric
study of the kinetics of DCCPS homopolymerization
showed that the reaction order is 0.5 with respect to the
initiator and 1 with respect to the monomer (similarly
to ). This means that the DCCPS copolymerization
with MMA should follow the same relationships as
the radical-chain polymerization of vinyl monomers.
Indeed, the elemental compositions of DCCPS and of
the copolymer synthesized conﬁ rm that the copolymers
can consist of different combinations of the monomeric
With the aim to determine the structure of the
copolymers formed, we examined the polymer spectra.
Comparison of the IR spectra of the copolymers
with those of the starting monomers revealed strong
absorption bands at 1720 cm
, characterizing the
stretching vibrations of the carbonyl group (for MMA).
In addition, the IR spectra of the copolymers contain