ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 7, pp. 1213!1219. C Pleiades Publishing, Ltd., 2008.
Original Russian Text C S.S. Ivanchev, O.N. Primachenko, V.N. Pavlyuchenko, S.Ya. Khaikin, V.A. Trunov, 2008, published in Zhurnal Prikladnoi
Khimii, 2008, Vol. 81, No. 7, pp. 1134!1140.
AND POLYMERIC MATERIALS
Proton-Conducting Membranes Based
on Multicomponent Copolymers
S. S. Ivanchev, O. N. Primachenko, V. N. Pavlyuchenko, S. Ya. Khaikin, and V. A. Trunov
St. Petersburg Branch, Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences,
St. Petersburg, Russia
Konstantinov Institute for Nuclear Physics, Russian Academy of Sciences, Gatchina, Leningrad oblast, Russia
Received May 12, 2007
Abstract-Preparation of proton-conducting polymeric composites via copolymerization of multicomponent
monomeric systems using the interpenetrating polymer network preparation procedure is studied. The prod-
ucts are characterized by the protonic conductivity, water-retaining capacity, and mechanical properties.
The approach used allows fabrication of membranes with a reasonable protonic conductivity over the
temperature range 20390oC. A possibility of modification of the proton-conducting materials with small
additions of hydrolyzable organosilicon comonomers is analyzed. The structure of the resulting systems is
examined by small-angle neutron scattering.
Currently one could say that the principal types or
classes of proton-conducting polymeric membranes
for fuel cells take a clear shape . Primarily these
are perfluorinated polymers of the Nafion type and
composition- and structure-related polymeric com-
posites , polycondensation membranes based on
poly(benzimidazoles), polyester3ester ketones, etc.
Recently data on proton-conducting polymeric
membranes based on hybrid polymeric systems were
reported . In this relation, patents and develop-
ments from the recently founded ITM Power Ltd.
are of particular interest . The original devel-
opment of this company proposes fabrication of not
only a membrane, but also a membrane electrode
assembly (MEA) consisting of electrodes and an ion-
exchange polymeric membrane (PM) made of a hy-
drophilic polymer bearing a strong ionic group.
Such an aggregate is prepared by g-radiation-
induced in situ copolymerization of a mixture of
hydrophobic and hydrophilic comonomers, includ-
ing a monomer containing a strong ionic group.
As the authors asserted, such PMs demonstrate high
protonic conductivity, controlled hydrophilicity, and
capability of recycling of the platinum catalyst from
MEA. Furthermore, the authors declare the pos-
sibility of reducing cost of PM and exploitation of
the system by an order of magnitude as compared to
Nafion membranes. They pointed out that cross-
linked polymeric membranes could be prepared
through not only radiation, but also chemical cross-
linking. The description of the invention includes no
data on the performance characteristics of the
membrane materials under different exploitation
In this study, we examined the possibility of im-
plementation of the method for fabricating polymer-
ic membranes, proposed in , including the
effect of the composition of the monomer mixture
on properties of the resulting PMs and their per-
formance characteristics as components of fuel cells
In synthesis of hydrophilic polymers containing
an ionic group, we used such monomers as acrylo-
nitrile (AN), N-vinylpyrrolidone (N-VP), vinyltri-
methoxysilane (VTMS), vinyltriethoxysilane (VTES),
3-(trimethoxysilyl)propyl methacrylate (TMSPMA),
(AMPSA), and ethylene glycol dimethacrylate
(EGDM), all from Sigma Aldrich.
The hydrophilic ionic polymers were synthesized
by copolymerization of three- or four-component