Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 8, pp. 1255−1258.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © G.N. Al’tshuler, N.V. Malyshenko, L.P. Abramova, S.Yu. Lyrshchikov, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85,
No. 8, pp. 1319−1323.
AND POLYMERIC MATERIALS
G. N. Al’tshuler, N. V. Malyshenko, L. P. Abramova, and S. Yu. Lyrshchikov
Institute of Coal Chemistry and Chemical Materials Science,
Siberian Branch, Russian Academy of Sciences, Kemerovo, Russia
Received May 29, 2012
Abstract—A new polymer was prepared by etheriﬁ cation of phenolic OH groups in polysulfotetraphenylcalix
resorcinolarene. It exhibits high ion-exchange capacity and is less hydrophilic than the starting polymer.
It is known  that the materials intended for
fabrication of nanoporous electrodes for fuel cells of
electrochemical generators should meet the following
requirements: porous structure; hydrophilic fragments in
combination with hydrophobic layers; catalytic activity
in hydrogen oxidation and oxygen reduction; high ionic
conductivity; stability in acidic media. It was shown 
that a palladium-containing nanocomposite based on
sulfonated polytetraphenylcalixresorcinolarene can
be used as catalyst for electrode processes in fuel cells.
Network polymers based on calixarenes combine the
hydrophilic and hydrophobic layers on the molecular
In this study we examined the possibility of controlling
the hydrophilic properties of polytetraphenylcalixres-
orcinolarene by varying pH of the medium and etherifying
hydroxy groups. For this purpose, we synthesized a new
polymer based on sulfotetraphenylcalixresorcinolarene
with a part of hydrogen atoms of phenolic OH groups
replaced by methyl groups. We studied the structure,
ion-exchange properties, and hydration of this polymer.
The polymer based on cis-tetraphenylcalix
resorcinolarene was prepared by catalytic resol
polycondensation with formaldehyde taken in 1 : 3 ratio,
followed by curing of the product according to . Excess
formaldehyde was separated with the mother liquor by
ﬁ ltration, and the granules obtained (d = 0.05–0.5 mm)
were washed with carbon tetrachloride, alcohol, and
water. The polymer is insoluble in alcohols and water
and has a 3D structure.
Polysulfotetraphenylcalixresorcinolarene I was
prepared by double sulfonation of the polymer derived
from cis-tetraphenylcalixresorcinolarene according
to . A study  involving PM3 calculations of model
structures, Fourier transform IR analysis, potentiometric
titration, determination of the ion-exchange capacity, and
elemental analysis showed that sulfo groups in I are ar-
ranged with high probability in phenyl substituents. The
suggested structure [4, 5] of the elementary unit of poly-
sulfotetraphenylcalixresorcinolarene I is shown below: