ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 8, pp. 1350!1353. + Pleiades Publishing, Inc., 2006.
Original Russian Text + A.I. Vorob’eva, M.N. Gorbunova, V.Yu. Gusev, S.I. Kuznetsov, S.V. Kolesov, V.P. Begishev, A.G. Tolstikov, Yu.B. Monakov,
2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 8, pp. 1363 !1366.
AND POLYMERIC MATERIALS
Copolymerization of N,N-Diallyl-N<-benzoylhydrazine
with Acrylonitrile and Sulfur Dioxide
A. I. Vorob’eva, M. N. Gorbunova, V. Yu. Gusev, S. I. Kuznetsov, S. V. Kolesov,
V. P. Begishev, A. G. Tolstikov, and Yu. B. Monakov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, Perm, Russia
Received March 7, 2006
Abstract-Radical copolymerization of N, N-diallyl-N`-benzoylhydrazine with acrylonitrile and sulfur dioxide
was studied. The kinetic features of the copolymerization of these systems were examined, the relative ac-
tivities of the monomers were determined, and the structure of the resulting copolymers was elucidated.
Polyfunctional polymers based on nitrogen-, oxy-
gen-, and sulfur-containing vinyl and allyl monomers
are of doubtless interest owing to their complexing
and flocculating properties and to a wide spectrum
of biological activities. These compounds are used
as flocculants, growth-stimulating agents in plant
growing, drugs in cattle breeding, aftertanning agents
in leather production, etc. . At the same time,
the range of monomers commercially available in
Russia for the synthesis of such polymers by radical
(co)polymerization is very limited. Therefore, applica-
tion of industrial facilities intended for production
of specialty products (in particular, hydrazine deriv-
atives) to the synthesis of N-containing monomers
and to production on their basis of new structural
types of polyfunctional polymers is a topical prob-
lem. Previously we have shown that copolymers of
diallylhydrazines with vinyl monomers and sulfur
dioxide can be, in principle, obtained .
This study deals with the radical copolymerization
of N, N-diallyl-N`-benzoylhydrazine (DABH) with ac-
rylonitrile and sulfur dioxide.
N,N-Diallyl-N`-benzoylhydrazine was prepared by
the reaction of benzoylhydrazine with allyl chloride:
3Cl + NH
The synthesis conditions are described in .
The purity was checked by elemental analysis and
C NMR spectroscopy.
Elemental composition, % C H N
Found 71.71 7.93 12.84
Calculated 72.22 7.41 12.96
The chemical shifts (d, ppm) and multiplicities of
signals in the
C NMR spectrum of DABH are listed
in the table (the
C NMR spectrum of the DABH3
copolymer was reported in ).
The comonomer (acrylonitrile, AN), initiators [azo-
bis(isobutyronitrile), AIBN; benzoyl peroxide, BP],
and solvents (dimethyl sulfoxide, DMSO; methanol;
acetone] were purified by standard procedures, and
their characteristics agreed with reference data. Sulfur
dioxide was dried by passing through concentrated
and freshly calcined CaCl
The copolymerization of DABH with AN and SO
was performed to low conversions in the bulk and
in DMSO in the presence of AIBN in evacuated am-
pules (with AN) or in a glass reactor  (with SO
The reaction mixture temperature was 80oC. The poly-
mers were purified by twofold reprecipitation from
the solvent (DMSO) into the precipitant (methanol
with AN, acetone with SO
). The purified polymers
were vacuum-dried to constant weight at 50oC.
The composition of the copolymers was calculated
from the results of elemental analysis.