ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 8, pp. 1384!1387. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + Yu.N. Pozhidaev, N.S. Shaglaeva, O.V. Lebedeva, S.S. Bochkareva, A.P. Safronov, M.G. Voronkov, 2007, published in Zhurnal
Prikladnoi Khimii, 2007, Vol. 80, No. 8, pp. 1346!1349.
AND POLYMERIC MATERIALS
Copolymers Based on Products of Base Hydrolysis
of Tetraethoxysilane in the Presence of Poly-N-vinylazoles
Yu. N. Pozhidaev, N. S. Shaglaeva, O. V. Lebedeva, S. S. Bochkareva,
A. P. Safronov, and M. G. Voronkov
Irkutsk State Technical University, Irkutsk, Russia
Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received May 2, 2007
Abstract-The products of base hydrolysis of tetraethoxysilane in the presence of polymeric nitrogen bases
poly-1-vinylpyrazole, poly-1-vinylimidazole, poly-4-vinylpyridine, and poly-2-methyl-5-vinylpyridine were
isolated. The conditions of their formation, chemical composition, structural characteristics, and sorption
properties with respect to noble metals (Ag, Au, Pt, and Pd) were studied. These products are highly dispersed
thermally stable interpenetrating copolymers poorly soluble in water and organic solvents. Their composition
and properties are governed by the kind of the polymeric nitrogen base.
Hybrid organic-inorganic composite materials con-
taining an inorganic component (silicon, titanium,
tin, zirconium, or aluminum oxide) chemically bound
with an organic component are widely used in various
field of science technology. The development of meth-
ods for preparing such materials and studies of their
properties contribute to the development of chemistry
and technology of nanomaterials .
An actively developing method for preparing hybrid
organic-inorganic materials and coatings is based on
a sol3gel process involving hydrolysis of alkoxysi-
lanes in the presence of organic compounds [4, 5].
Currently the sol3gel technology is the main tech-
nique for purposeful synthesis of hybrid silicate and
silica-carbonaceous materials (nanomaterials, coat-
ings, membranes, sorbents, biologically active com-
pounds, catalysts, etc).
It was reported in  that, in the first stage of hy-
drolysis of tetraethoxysilane in ethanol in the presence
of polyvinylbutyral, poly-1-vinylimidazole, poly-4-
vinylpyridine, or poly-1-vinyl-2-pyrrolidone, a homo-
geneous solution is formed. In further prolonged stor-
age, these solutions become gelatinous and then solid
compounds precipitate. It is believed that the supra-
molecular structure of these compounds is stabilized
by numerous hydrogen bonds between the silanol
groups and the electron-donor atoms (N, O) of the or-
ganic polymers. The sorption capacity of these ma-
terials for Cu
varies from 25 to 280 mg g
In this study, we isolated highly dispersed hybrid
organic3inorganic composite materials by hydrolysis
of tetraethoxysilane in the presence of poly-1-vinyl-
azoles and polyvinylpyridines and examined their
structural characteristics and thermal and chemical
stability. These materials were also tested as sorbents
for noble metal ions.
1-Vinylpyrazole and 1-vinylimidazole were pre-
pared by the reaction of pyrazole or imidazole with
acetylene, as reported in [7, 8].
The commercial monomers 4-vinylpyridine and
2-methyl-5-vinylpyridine were purified by vacuum
Poly-1-vinylpyrazole (PVPz), poly-1-vinylimidazole
(PVIm), poly-4-vinylpyridine (PVPy), and poly-2-
methyl-5-vinylpyridine (PMVPy) were prepared by
polymerization of the respective monomers by
the methods reported in [9, 10].