Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 8, pp. 1355−1359.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
V.V. Tereshatov, V.Yu. Senichev, V.N. Strel’nikov, S.F. Krasnosel’skikh, M.A. Makarova, 2010, published in Zhurnal Prikladnoi
Khimii, 2010, Vol. 83, No. 8, pp. 1249−1253.
New High-Density Environmentally Clean Polyurethane
Materials with Binary Plasticizers
V. V. Tereshatov, V. Yu. Senichev, V. N. Strel’nikov, S. F. Krasnosel’skikh,
and M. A. Makarova
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
Received March 11, 2010
Abstract—Thermal and physicomechanical properties of thermoplastic polyurethane binders plasticized with
mixtures of low-melting diurethanes with low-molecular-weight liquids were studied. Regular trends in the effect
of components of mixed plasticizers on the properties of polyurethane thermoplastics ﬁ lled with ﬁ nely dispersed
tungsten were revealed.
One of promising directions of physical modiﬁ cation
of segmented thermoplastic polyurethane materials is
the use in their composition of low-melting diurethane
compounds formed by reactions of diisocyanates with
monohydric alcohols and having the melting point T
below 100°С .
At temperatures above the melting point,
diurethanes are effective plasticizers of thermoplastic
polyurethanes (TPUs), allowing 50–70°C decrease
in the thermoplastic processing temperature and
preparation of high-density environmentally clean
polyurethane materials ﬁ lled with ﬁ nely dispersed
tungsten for the radiation protection of various objects
[1, 2]. However, the glass transition point of the ﬂ exible
, of such TPUs with low-melting diurethane
is no lower than –30°С, which limits the possibility
of using them under natural climatic conditions. The
use of low-molecular-weight liquids with a low glass
transition point Т
as polyurethane plasticizers ensures
low glass transition point of the polymeric matrix,
but the strength properties of the material in this case
become considerably worse [3, 4].
Here we suggest an approach to the preparation
of high-density TPUs using mixtures of low-melting
diurethanes with liquids having low glass transition
The goal of this study was to reveal regular trends
in the effect of individual plasticizers and their
mixtures with diurethanes on the frost resistance and
physicomechanical characteristics of polyurethane
binders and ﬁ lled composites based on them and to
develop high-density TPUs capable to operate in the
temperature interval from –40 to +50°С.
Plasticized thermoplastic polyurethane binders and
polyurethane composites based on them with high degree
of ﬁ lling with ﬁ nely dispersed tungsten were prepared
by a two-step procedure. In the ﬁ rst step, we prepared
a prepolymer by the reaction of 4,4'-diphenylmethane
diisocyanate with oligo(tetramethylene oxide)diol
(М ~ 1000, 1400) at 2.55-fold excess of NCO groups. In
the second step we prepared a thermoplastic polyurethane
by the reaction of the prepolymer with 2,4-butanediol
(NCO : OH ratio in the experiments was 0.97 or 0.99).
Low-melting plasticizers were introduced into the
reaction mixture in the form of a melt or a solution in
liquid plasticizers. In the process, the reaction mixture
was heated to a temperature exceeding by 10–15°C the
melting point of the diurethane. As a ﬁ ller we used two
fractions of ﬁ nely dispersed tungsten with the particle
size of 18–22 (70%) and 4–8 μm (30%).