1070-4272/03/7611-1844$25.00C2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 11, 2003, pp. 1844!1849. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 11,
2003, pp. 1895!1900.
Original Russian Text Copyright + 2003 by Suvorov, Dul’tseva, Ovchinnikova, Khrustaleva, Ostanina, Abramova.
AND POLYMERIC MATERIALS
Preparation and Properties of Polymers Derived
from Epoxy Resins and Oligochelatotitanophenylenesiloxanes
A. L. Suvorov, L. D. Dul’tseva, G. I. Ovchinnikova, E. A. Khrustaleva,
N. Yu. Ostanina, and V. I. Abramova
Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences, Yekaterinburg, Russia
Received April 14, 2003
Abstract-Oligochelatotitanophenylenesiloxanes of various structures were suggested as curing agents for
epoxy resins. The compound formulas and curing conditions were chosen so as to ensure the maximal degree
of cross-linking and hence the best physicomechanical properties of the polymers.
Preparation of polymers derived from epoxy resins
and oligochelatotitanoarylenesiloxanes of the general
where Ch is a chelating ligand and Ar is phenylene,
p,p`-diphenylene, or p,p`-oxydiphenylene, was re-
ported in .
In this work we studied the reactions of oligoche-
latotitanoarylenesiloxanes with epoxy resins and the
properties of the resulting polymers as influenced by
the chemical structure of the curing agent and its
content in the compound.
Experiments were performed with ED-20 epoxy3
4,4`-isopropylidenediphenol resin (epoxide number
21.3), which was purified by filtration followed by
vacuum drying, and oligochelatotitanoarylenesilox-
anes prepared by heterofunctional condensation of
bis(dimethoxysilyl)benzene with appropriate bis(che-
lato)dialkoxytitanium . The characteristics of the
oligochelatotitanoarylenesiloxanes prepared are listed
in Table 1.
We found that the compounds containing various
amounts of oligochelatotitanoarylenesiloxanes do not
lose solubility after prolonged (for up to a year) stor-
age at room temperature. However, in the course of
storage, as in the case of epoxy3titanopolyether com-
pounds [3, 4], their viscosity grows, though to a con-
siderably lesser extent (Fig. 1). This may be due both
to chemical reactions of the epoxy groups with the
functional groups of the curing agent and to inter-
molecular interaction of the components [4, 5].
Curing of epoxy3chelatotitanophenylenesiloxane
compounds starts at a noticeable rate at 1603200oC
depending on the structure of the curing agent and its
content in the compound. The process is manifested as
a sharp ascent in the DTA curves . Since curing of
epoxy resins is an exothermic process, the compounds
were heated stepwise from 150 to 200 or 220oC de-
pending on the curing agent content. The curing time
at each temperature was varied from 1 to 6 h, so as to
ensure the maximal degree of cross-linking (content of
soluble fraction <2%) and obtain high-quality cavity-
free samples (Table 2).
The reaction of oligochelatotitanoarylenesiloxanes
with the epoxy resin was studied by IR spectroscopy.
Compounds were heated in a chosen stepwise curing
mode, and at each temperature samples were taken to
record the spectrum. Changes in the spectra became
noticeable at 170oC. The bands at 920 and 865 cm
characteristic of the epoxy group , decreased in
intensity and fully disappeared at 200oC. In the range
, there are also bands originating from
Fig. 1. Variation of the viscosity h in the course of stor-
age at room temperature of epoxy compounds based on
(1, 2) oligomer I and (3) titanium polyether. (t) Time.
Curing agent content, %: (1, 3) 10.0 and (2) 20.0.