Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 8, pp. 1372−1379.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
E.R. Volkova, V.V. Tereshatov, Zh.A. Vnutskikh 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 8, pp. 1266−1273.
Formation of Polyurethane Structural Materials
Based on Mixtures of Oligoethers with Different Reactivities
E. R. Volkova, V. V. Tereshatov, and Zh. A. Vnutskikh
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
Received February 27, 2010
Abstract—Kinetics of the reaction of urethane formation from oligopolyols with primary and secondary hydroxy
groups and the inﬂ uence exerted on their interaction by products formed in the reaction of N,N,N',N'-tetrakis-
(-2-hydroxypropyl)-ethylenediamine with an isocyanate were studied. Samples of high-strength polyurethane
composites based on mixtures of oligoetherpolyols and the oligomeric diamine were obtained. These samples
approximately twice surpass in strength materials based on oligoepoxides. The working capacity of the samples
under severe climatic conditions was demonstrated.
The presently existing approaches to study,
analysis, and control of the structure and properties of
polyurethanes (PUs) are commonly related to elastic
microheterogeneous segmented polyurethanes used
to produce block articles. Block-structure micro-
heterogeneous polyurethane materials cannot be used
to fabricate high-strength rigid constructions. At a high
concentration of hard blocks, the structure of segmented
polymers is weakened by a large number of defects
constituted by inclusions of a low-strength soft phase.
In the structural-kinetic approach used to study how
hard polymeric materials are formed, the process yielding
a material is regarded as formation of a heterogeneous
system composed of a continuous cross-linked polymer
matrix within which regions of a loose network and
unreacted components are dispersed. The polymer
matrix is inhomogeneous and is constituted by cross-
linked microgels and agglomerates. It has been shown
[1, 2] that the higher the rate of gelation reactions, the
more inhomogeneous the structure of the material.
Constructing a prescribed regular structure of segmented
polyurethanes is not too difﬁ cult if the polyurethanes
are produced in the presence of a volatile solvent [3,
4]. The approach with volatile solvents is unacceptable
for fabrication of monolithic rigid polyurethane articles.
A regular structure should be constructed in another
Of fundamental importance for fabrication of elastic
high-strength polyurethane constructions rapidly cured
at room temperature is the original choice of hydroxy-
containing oligomers. The glass transition temperature
of the structural material should be not lower than 25°C
to provide its operation in working areas and not lower
than 50°C for natural climatic conditions.
The goal of our study was to develop an approach to
formation of high-strength rapidly cured polyurethane
low-temperature-cure composites and to implement
this approach for the example of a material operative in
constructions working under severe climatic conditions.
Our approach is based on a successive construction
of a prescribed structure of a polyurethane composite
by using a mixture of polyethers with primary and
secondary hydroxy groups, combined with a catalytically
active polyol, N,N,N'N'-tetrakis-(-2-hydroxypropyl)
ethylenediamine (Lapramol 294).
To solve the problem, we used a wide variety of