Modification of Polyvinyl Chloride with Na(K) Salts
of 1,2,4-Triazole and 1,2,3-Benzotriazole
T. G. Ermakova, N. P. Kuznetsova, L. I. Volkova, and G. F. Myachina
Favorskii Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, Irkutsk, Russia
Received August 5, 2008
Abstract—The possibility of polyvinyl chloride modification by nucleophilic substitution of chlorine with
sodium and potassium salts of 1,2,4-triazole and 1,2,3-benzotriazole in dimethylformamide at 40–80°C was
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 3, pp. 488–491. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © T.G. Ermakova, N.P. Kuznetsova, L.I. Volkova, G.F.Myachina, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 3,
Polyvinyl chloride (PVC) is one of the most
important, readily available, and cheap large-tonnage
polymers. It exhibits a set of valuable properties [1–3].
The growth of the PVC production is due to steady
expansion of its application fields . Owing to
limited solubility and low heat resistance of PVC,
processing and production of materials based on it is
impossible without effective additives (stabilizers and
plasticizers). The presence of the C–Cl bond allows
modification of PVC to obtain a wide range of
polymeric materials and articles with a new set of
valuable service properties.
PVC can be modified by nucleophilic substitution
of chlorine atoms using salts of various azoles [5, 6].
Compounds containing a triazole ring are used in
industry, agriculture, and medicine [7–9], in particular,
1,2,4-triazole is used as plasticizer .
The goal of this study was modification of
commercial PVC with sodium and potassium salts of
1,2,4-triazole and 1,2,3-benzotriazole in DMF, exa-
mination of the structure and physicochemical
properties of the copolymers, and development on their
basis of proton-conducting composites promising as
membranes for fuel cells.
We used commercial PVC, MM 70 000,
synthesized by the suspension procedure at the
Sayanskkhimplast Joint-Stock Company. Sodium and
potassium salts of 1,2,4-triazole and 1,2,3-benzo-
triazole were prepared by reactions of triazoles
preliminarily purified by recrystallization with alkali
metal hydroxides in absolute ethanol at 24°C. The
alcohol from the reaction mixture was removed, and
the salts were dried by azeotropic distillation of water
with benzene using a Dean–Stark trap. The purity of
the salts was evaluated by potentiometric titration.
Pure grade dimethylformamide was purified by the
known procedure .
Modification of PVC with Na(K) salt of triazoles
was performed in a four-necked flask equipped with a
stirrer, a reflux condenser, a capillary for feeding
argon, and a thermometer. The reactants in a DMF
solution were heated to 40–80°C. The molar ratio of
PVC and azole salts was 1 : 1 or 1 : 2 (Table 1). After
the process completion, the insoluble black precipitate
was separated by centrifugation, washed with water,
alcohol, and diethyl ether, and dried in a vacuum. The
reaction solution of the copolymer in DMF was poured
into water. The precipitated dark brown precipitate of
the copolymer was filtered off, washed with water to
disappearance of chloride ions, and dried in a vacuum
at 40°C to constant weight.
The IR spectra of the copolymers were recorded on
a Bruker IFS-25 spectrometer. Samples were prepared
as KBr pellets and mulls in mineral oil. The
spectra of samples with noise proton decoupling were
AND POLYMERIC MATERIALS