Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 7, pp. 1121−1124.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © M.N. Gorbunova, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 7, pp. 1155−1158.
AND POLYMERIC MATERIALS
Copolymerization of 2,2-Diallyl-1,1,3,3-tetraethylguanidinium
Chloride with Fumaric Acid
M. N. Gorbunova
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
Received February 22, 2012
Abstract—Radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with fumaric acid in
the bulk and in organic solvents was studied. The kinetic relationships of the reaction were examined, and the
relative activities of the monomers were determined.
Synthetic polyelectrolytes play an important role in
science, engineering, and medicine. They are widely used
as effective ﬂ occulants, coagulants, sorbents, extractants,
biocides, and carriers for biologically active substances
[1–4]. Previously we studied the copolymerization
of 2,2-diallyl-1,1,3,3-tetraethylguanidnium chloride
(AGC) with maleic acid (MA) . It seems interesting
to study the copolymerization of AGC with an isomer of
maleic acid, fumaric acid (FA), with the aim to assess
the principal possibility of preparing the copolymers
and to determine common and speciﬁ c features of the
copolymerization with the cis and trans isomers of the
was prepared by the procedure described in . The AGC
purity was checked by elemental analysis and
Analytical data, % (calculated values in parentheses):
С 62.42 (62.61), Н 10.67 (10.43), N 14.58 (14.61), and
Cl 12.32 (12.35). The chemical shifts δ (ppm) and mul-
tiplicities of the
С NMR signals of AGC are given in
Fumaric acid (Alfa Aesar) was used without additional
puriﬁ cation, mp 299°С. Its
C NMR data [δ (ppm) and
multiplicities] are given in Table 1. The initiator, AIBN
(analytically pure grade), was recrystallized three times
from methanol and vacuum-dried. The solvents used in
the study, after puriﬁ cation by standard procedures ,
had the characteristics consistent with the reference data.
Copolymerization of AGC with FA was performed in
the bulk and in organic solvents in the presence of AIBN.
The process kinetics was monitored gravimetrically.
After the required conversion was attained, the reaction
was stopped by cooling and subsequent precipitation of
the polymer into water. The copolymers were puriﬁ ed by
double reprecipitation from a solution in an organic sol-
vent into acetone and were dried in a vacuum at 40–50°С
to constant weight. The copolymer composition was
determined by elemental analysis.
The effective copolymerization constants r
were calculated by the Mayo–Lewis , Fineman–Ross
, and Kelen–Tüdös  methods.
С NMR spectra were recorded with a Varian
Mercury spectrometer (operating frequency 75.5 MHz)
with broadband proton decoupling and in the JMOD
mode. As solvent we used DMSO-d
The UV spectra were taken with an SF 2000 spec-
trometer at 20°С. The complex formation was judged
by comparing the optical density of solutions of the
individual monomers and their mixtures.
A study of the copolymerization of AGC with FA in
organic solvents at low conversions in the presence of
AIBN as initiator showed that, in contrast to the copo-
lymerization with MA , the copolymers formed have