Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 11, pp. 2015−2019.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
O.V. Lebedeva, Yu.N. Pozhidaev, R.G. Sultangareev, A.S. Pozdnyakov, S.S. Bochkareva, E.A. Orkhokova, N.S. Shaglaeva, 2009, published
in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 11, pp. 1869−1873.
AND POLYMERIC MATERIALS
Polymeric Electrolytes Based on Vinylpyridines
O. V. Lebedeva, Yu. N. Pozhidaev, R. G. Sultangareev, A. S. Pozdnyakov, S. S. Bochkareva,
E. A. Orkhokova, and N. S. Shaglaeva
Irkutsk State Technical University, Irkutsk, Russia
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received April 28, 2009
Abstract—Homopolymers of 4-vinylpyridine and 2-methyl-5-vinylpyridine and copolymers of 2-methyl-5-
vinylpyridine with vinyl chloride and vinyl acetate were prepared by radical copolymerization. Organo-inorganic
composites were prepared by hydrolytic polycondensation of the copolymers obtained and tetraethoxysilane. From
solutions of the (co)polymers and composites, films were prepared by casting, and their protonic conductivity
Membrane materials developed on the basis of
polymeric electrolytes find wide use in modern
technologies in puriﬁ cation of gases and liquids, their
separation, operation of fuel cells, and electrochemical
synthesis. By now, the best transport properties have
been attained for Naﬁ on-type perﬂ uorinated sulfonic
acid membranes initially developed for electrochemical
processes. In particular, these membranes and their
Russian analog, MF-4SK membranes (Plastpolimer
Joint-Stock Company, St. Petersburg), are widely used
for constructing fuel cells . However, practical use of
these membranes is largely restricted by their high cost.
Membranes based on polybenzimidazole doped with
phosphoric acid are also commercially available .
However, on contact of these membranes with water,
the acid–base complex decomposes, the phosphoric acid
is washed out, and therefore the protonic conductivity
Preparation of composite polyelectrolyte membranes
with inorganic additives is considered as one of the
ways to improve mechanical properties, enhance the
heat resistance, and weaken the dependence of the
electrotransport characteristics on the humidity .
In this study we prepared (co)polymers and organo-
inorganic composites based on vinylpyridines and
evaluated their electrical conductivity.
4-Vinylpyridine (VP), 2-methyl-5-vinylpyridine
(MVP), and vinyl acetate (VA) are commercial
monomers. They were puriﬁ ed by vacuum distillation.
Vinyl chloride (VC) was used without puriﬁ cation. The
purity of the monomers was checked by measuring their
constants (Table 1). Homopolymers of VP (PVP) and
MVP (PMVP) were prepared by published procedures
. Homopolymerization of systems of MVP with VC
and VA was performed under the conditions of radical
initiation with azobis(isobutyronitrile) at 60°С. Weighed
portions of reactants were charged into ampules. After the
copolymerization completion, the cooled ampules were
opened, and the reaction mixture MVP–VC or MVP–VA
was dissolved in DMF. The copolymer was precipitated
with ice-cold water. The products were dried in a vacuum
to constant weight. The copolymers were reprecipitated
The viscosity of dilute copolymer solutions was
measured with an Ubbelohde capillary viscometer at
25°С. Elemental analysis of reaction products was
performed with a Thermo Finnigan gas analyzer. The
IR spectra of copolymers were taken with a Specord IR-
75 spectrometer from KBr pellets and mulls in mineral
oil, and also with a Bruker IFS-25 spectrometer. The
С NMR spectra of copolymer samples were recorded