Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 9, pp. 1600−1606.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © I.Yu. Ruskol, E.I. Alekseeva, N.S. Ponkratova, V.V. Kireev, A.A. Savchenko, S.R. Nanush’yan, 2011, published in Zhurnal Prikladnoi
Khimii, 2011, Vol. 84, No. 9, pp. 1551−1557.
AND POLYMERIC MATERIALS
Control of Mechanic Properties of 3D Network Polymers
Based on Vinyl and Hydride-containing Siloxanes
I. Yu. Ruskol
, E. I. Alekseeva
, N. S. Ponkratova
, V. V. Kireev
A. A. Savchenko
, and S. R. Nanush’yan
Mendeleev Russian University of Chemical Engineering, Moscow
State Research Institute of Chemistry and Technology of Organoelemental Compounds, Moscow
Received December 24, 2010
Abstract—The catalytic hardening of siloxane oligomers containing equivalent amount of hydride and vinyl
groups in the linear and cyclic fragments of the oligomers was investigated and the effect of the position of these
groups on the strength of the 3D network polymers was demonstrated..
Siloxane thermoreactive oligomers are under
constant attention due to their growing application
in various ﬁ elds of the modern technology. The main
synthetic procedure of their preparation remains the
hydrolytic polycondensation of polyfunctional silanes.
The structure of these oligomers can be described by
the general formula [RSi(OH)
the n and m values depend on the ratio of the tri- and
bifunctional silanes in the initial mixture for hydrolysis,
and x depends on the extent of the silanol condensation.
At the thermal hardening of these oligomers
volatile products (water) are liberated and a spatial
network forms which may be tentatively represented
as consisting of siloxane rings of various size: primary,
formed at the stage of the hydrolytic polycondensation,
and secondary, formed through the interaction of silanol
groups in the hardened oligomer .
The formation of various cyclosiloxane groups during
the thermal hardening of oligomethylsilsesquioxanes
(OMSSO) was postulated  and it was conﬁ rmed by
the analysis of IR spectra of polymethylsilsesquioxanes
(PMSSO) obtained from OMSSO. It was also shown in
 that the heating of PMSSO in an inert atmosphere
at 500–700°С was accompanied by hydrogen liberation
and the formation in the solid thermolysis products
Si≡ and ≡SiCH
Si≡ bond which were
precursors of the elements of silicon carbide structures.
In this study the processes of the catalytic hardening
of siloxane oligomers containing vinyl and hydride
groups were investigated.
The hydrosylilation reaction was not accompanied
with volatiles liberation, the hardening proceeded at
100–150°С, whereas the oligomers of the condensation
type required for hardening the temperature of 200°С
and more. At the hardening of oligomers using the
hydrosilylation reaction the formed 3D network is
constructed of two types of bonds: siloxane and carbon-
carbon bonds. Oligomers of such type were described
in the literature, and the advantages of the coatings
based on them were indicated, such as thermal stability,
strength, resistance to gasoline, and the stability in a
high vacuum . Polymers obtained by the hardening