ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 4, pp. 554−558. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © I.A. Blinov, V.M. Belokhvostov, A.A. Kossoy, D.A. Mukhortov, M.P. Kambur, O.V. Lantratova, E.S. Kurapova, 2016, published in Zhurnal
Prikladnoi Khimii, 2016, Vol. 89, No. 4, pp. 437−441.
INORGANIC SYNTHESIS AND INDUSTRIAL
Abstract—Formal kinetic model is suggested on the basis of experimental studies of the heat-release kinetics in
decomposition of an anion-exchange resin, copolymer of N-methyl-4-vinylpyridinium chloride and divinylbenzene.
The model makes it possible to determine the service life of the resin in the temperature range 100–170°C in opti-
mization of the process in which monosilane is synthesized from trichlorosilane with the resin used as a catalyst.
Thermal Decomposition of Anion-Exchange Resin
Based on Copolymer of 4-Vinylpyridine
I. A. Blinov, V. M. Belokhvostov, A. A. Kossoy, D. A. Mukhortov, M. P. Kambur,
O. V. Lantratova, and E. S. Kurapova
FSUE RSC “Applied Chemistry,” ul. Krylenko 26А, St. Petersburg, 193232 Russia
Received November 11, 2015
is used in chemical-vapor deposition
processes to manufacture semiconductor articles. The
most widely used method for synthesis of SiH
catalytic disproportionation of trichlorosilane SiHCl
the gas phase at a temperature of 100–160°C, with the
role of a catalyst played by anion-exchange resins based
on vinylpyridine and its homologs: foreign (Amberlyst
and domestic strongly basic resins of VP brands (VP-1p,
VP-3Ap). Thermodynamic calculations and experimental
results indicate that the yield of SiH
in equilibrium, as
is commonly the case in production of monosilane, does
not exceed 2–4% . Because the disproportionation
reaction occurs with absorption of heat and is reversible,
raising the temperature in the reaction zone results in that
the yield of monosilane grows. However, similarly to any
organic compounds, anion-exchange resins are subject to
thermal destruction at elevated temperatures.
Therefore, a still topical problem consists in optimizing
the synthesis process of monosilane on anion-exchangers
as catalysts, i.e., in ﬁ nding the optimal temperature of the
disproportionation reaction, at which the anion exchanger
is stable or its decomposition is negligible and the yield
of monosilane is at a maximum. For this to be done, it is
necessary to study the thermal resistance of the resins at
At present, a limited number of anion exchangers
are manufactured in Russia. One of these is the anion
exchanger of VP-3Ap brand, produced on the basis of
the available monomer, 4-vinylpyridine. In the polymer,
4-vinylpyridine is partly in the form of N-methyl-4-
vinylpyridine chloride, the fraction of which is 15–
19 wt % in terms of chloride ions. The anion exchanger
contains 10 wt % technical-grade divinylbenzene as the
Previously, the thermal stability of anion exchangers
has been only studied at temperatures below 100°C [2, 3].
Therefore, the results obtained give no way of constructing
a formal-kinetic model suitable for calculating the thermal
destruction of VP-3Ap resin at temperatures higher than
100°C. Therefore, developing a kinetic model of thermal
destruction of the resin, required for ﬁ nding the minimum
operating expenditure in production of monosilane, is a
rather topical task.
To develop a kinetic model, we studied the thermal
resistance of the resin at temperatures higher than 100°C
with two heat-ﬂ ow Setaram calorimeters, S-80 and DSC-
TG-111. The experiment control and experimental data
processing were performed using the Eksperiment and
TDPro software developed at Cheminform Ltd.
Experiments were performed in ampules made of
various materials (glass, stainless steel, and ceramics),