Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 8, pp. 1345−1351.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
V.V. Tereshatov, M.A. Makarova, V.N. Strel’nikov, E.R. Volkova, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 8,
Frost-Resistant Polyurethane Compositions
with a Low Temperature Coefﬁ cient
of Young’s Modulus
V. V. Tereshatov, M. A. Makarova, V. N. Strel’nikov, and E. R. Volkova
Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, Perm, Russia
Received April 5, 2010
Abstract—Single-phase and microheterogeneous unplasticized and plasticized polyurethane compositions based
on oligo(diisocyanates) and their blends were synthesized. The frost resistance and temperature dependence of
Young’s modulus were examined for these materials in relation to their structural organization.
High wear resistance, strength, and elasticity, as well
as bio- and hemocompatibilities, make polyurethane
elastomers suitable for diversiﬁ ed industrial and
medicinal applications. A prominent place among these
compounds is occupied by to the so-called segmented
polyurethanes (SPUs) consisting of alternating soft and
hard blocks. Due to a strong difference in polarities
of these blocks (segments) they undergo microphase
segregation with formation of domains of 5–50-nm hard
blocks [1, 2]. Hard blocks are yielded by the reaction
of diisocyanate with low-molecular-weight diol or
diamine. In the absence of such reactants, single-phase
polyurethanes are typically formed that do not contain
extended hard blocks . The properties of polyurethane
materials essentially depend on the chemical structure
of the oligomers used, as well as on the concentration of
the hard blocks and their solubility in the soft polymer
Since recently, much attention has been devoted
to polymers serviceable under the Far North and the
Arctic conditions , in particular, to frost-resistant
polyurethane materials . Of much signiﬁ cance for
application under natural climatic conditions are stable
physicomechanical properties of materials over a broad
range of negative temperatures. This is particularly
pertinent to Young’s modulus (secant modulus of an
elastomer under 100% strain), because under real
application conditions, in particular under cyclic loading,
the strain of the material typically does not exceed
100%. A not very high Young’s modulus of elastomers
at negative temperatures is essential, e.g., for pressure
regulators on gas pipelines, as well as for a number of
elastic elements of transport and industrial equipment
(traversing gear parts, sealing couplings, gaskets).
Thus, synthesis of polyurethanes with low glass
transition temperatures and low temperature coefﬁ cients
of Young’s modulus is topical for elastomers to be
applied at negative temperatures.
Here, we established a correlation between the structure
and Young’s modulus of polyurethane elastomers over
a broad range of positive and negative temperatures.
We synthesized polyurethane compositions with glass
transition temperatures to –80…–90°С and temperature
coefﬁ cient of Young’s modulus no larger than 4 in the
–60…–25°С temperature range.
A series of plasticized and unplasticized binders with
individual and mixed soft segments were synthesized.
In our experiments we used oligo(butadiene)diol
(OBD) with M ~ 1000, oligo(tetramethylene oxide)diol,
polyfurite (PF) with M ~ 1000 (PF-1000), M ~ 1400 (PF-
1400), and M ~ 2000 (PF-2000), oligo(propylene oxide)
diol with M ~ 2000 (Laprol 2102) and a trifunctional
addition product of trimethylolpropane, propylene