1070-4272/05/7809-1549+2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 9, 2005, pp. 1549!1551. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 9,
2005, pp. 1574!1576.
Original Russian Text Copyright + 2005 by Shoinbekova, Nikitina, Zhunusova, Mukhitdinova, Ergozhin.
Effect of Initiator on the Microstructure of Copolymers
of Acrylic Acid with a Disubstituted Derivative
of Monoethanolamine Vinyl Ether and Chloranil
S. A. Shoinbekova, A. I. Nikitina, G. N. Zhunusova,
B. A. Mukhitdinova, and E. E. Ergozhin
Bekturov Institute of Chemical Sciences, Ministry of Education and Science of Kazakhstan Republic,
Received June 7, 2005
Abstract-The influence of the initiator on the copolymerization of acrylic acid with a disubstituted deriva-
tive of monoethanolamine vinyl ether and chloranil was examined.
The structure and properties of copolymers depend
on the synthesis conditions, in particular, on the initi-
ator used . Numerous studies concern the relative
activity of various monomers in copolymerization, but
the effect of initiator on these parameters is consid-
ered only in a few of them [2, 3]. In this connection,
it is interesting to study the reactivity of a new mono-
mer derived from monoethanolamine vinyl ether and
chloranil (MEAVE3CA3MEAVE)  in the reaction
with acrylic acid (AA) in the presence of various initi-
ators. The copolymers thus obtained exhibit redox,
complexing, and ion-exchange properties and show
promise as ion exchangers.
In this study we examined how the initiator af-
fects the relative activity of the monomers and the
composition and microstructure of the copolymers in
the copolymerization of MEAVE3CA3MEAVE with
MEAVE3CA3MEAVE was prepared as described
in . Dimethylformamide (DMF) was purified by
the standard procedure . The initiators, azobis(iso-
butyronitrile) (AIBN, mp 1023103oC) and potassium
persulfate (PP), were recrystallized from absolute
methanol and water, respectively .
The copolymerization was performed by an ampule
method. The starting components were loaded in one
portion. The mixture contained 6 wt % initiator
(AIBN or PP) relative to the sum of the monomers.
The reaction was performed at 78oC. The MEAVE3
CA3MEAVE concentration was 20 g l
. The solvent
was DMF in the case of AIBN and DMF : water (2 : 3
by volume) in the case of PP. The molar ratio of the
monomers was varied from 20 : 80 to 80 : 20. The
conversion was estimated from the concentrations of
the unchanged monomers, which were determined
polarographically (MEAVE3CA3MEAVE) and by
The polarograms were taken in 25% DMF, with
phosphate buffer solution (pH 7.4) as supporting elec-
trolyte, at 25+0.5oC on a PU-1 polarograph with a
mercury dropping electrode (open-circuit capillary
= 4.38 mg
. As refer-
ence electrode we used saturated calomel electrode.
The solutions were deoxygenated by bubbling with
The polymer structure is primarily determined by
the initiation procedure and by chain propagation and
termination reactions . The initiation affects the
copolymer composition and the configuration of
monomeric units. The choice of the initiator is most
frequently governed by its solubility in the monomer
or in the solvent and by the temperature at which the
required rate of generation of free radicals can be
attained. The initiators usually used for preparing co-
polymers of vinyl ethers with styrene and acrylic and
other monomers are peroxides and azo compounds
. In copolymerization of MEAVE3CA3MEAVE
with acrylic acid, we used AIBN and PP inducing the
polymerization by the free-radical mechanism.
Using the Mayo3Lewis integral equation of the
copolymer composition , we calculated the copoly-