ISSN 1070-4272, Russian Journal of Applied Chemistry, 2018, Vol. 91, No. 12, pp. 1937−1944.

© Pleiades Publishing, Ltd., 2018.

Original Russian Text © V.N. Strel’nikov, V.Yu. Senichev, A.I. Slobodinyuk, A.V. Savchuk, E.R. Volkova, M.A. Makarova, Yu.L. Belov, L.F. Derzhavinskaya,
D.G. Selivanova, 2018, published in Zhurnal Prikladnoi Khimii, 2018, Vol. 91, No. 12, pp. 1708−1716.
MACROMOLECULAR COMPOUNDS
AND POLYMERIC MATERIALS

Preparation and Properties of Frost-Resistant Materials

Based on Compounds of Oligoether Urethane Epoxides
and Diglycidyl Urethane
V. N. Strel’nikova, V. Yu. Senicheva, A. I. Slobodinyuka,*, A. V. Savchuka,
E. R. Volkovaa, M. A. Makarovaa, Yu. L. Belova,
L. F. Derzhavinskayaa, and D. G. Selivanovaa
a Institute of Technical Chemistry, Branch of the Perm Federal Research Center, Ural Branch,
Russian Academy of Sciences, Perm, Russia
*e-mail: [email protected]

Received April 28, 2018

Abstract—A procedure was suggested for preparing epoxy ether urethane oligomers via intermediate oligodi-
isocyanates with increased content of the starting 2,4-toluene diisocyanate. The procedure allows preparation of
epoxy-containing oligomers with appreciable fraction of low-molecular-mass diglycidyl urethane. The presence
of diglycidyl urethane in the binder enhances not only the adhesion but also the strength of the cured material
without significantly affecting the glass transition point of the binder. Elastic materials prepared by curing the
compounds studied with cylcoaliphatic amines exhibit enhanced levels of strength and low-temperature elasticity.
Keywords: epoxy urethane oligomers, strength, adhesion, critical strain
DOI: 10.1134/S1070427218120042

Owing to good adhesion, dielectric, and mechanical satisfactory frost resistance, with the glass transition
characteristics, elastic compounds based on epoxy point reaching –76°С [16]. A significant drawback of
urethane oligomers (EUOs) containing urethane groups such materials is low strength, no higher than 5 MPa.
in the chain and terminal epoxy groups are used as It is known that the strength of EUO-based materials
adhesives [1–5], base of casting compounds for various can be enhanced by introducing a certain amount of
purposes, resistant to moisture and aggressive media [6– epoxy–4,4'-isopropylidenediphenol resins [17], but
10], and components of biodegradable materials [11]. such modification, as a rule, gives rise to problems with
EUOs are synthesized from oligomeric diols, ensuring the required deformability of the material,
diisocyanates, and epoxy alcohols. As a rule, the which is particularly important at low temperatures.
synthesis is performed in two steps. The first step We believe that a frost-resistant elastic material with
involves the reaction of oligomeric diol with diisocyanate high mechanical characteristics can be prepared using
to form oligomeric diisocyanate, and the second step, polyether urethane epoxides, which have the glass
the reaction of this product with epoxy alcohol [12–15]. transition point below –70°С but are characterized by
The resulting EUOs are cured with amines, dicarboxylic considerably higher level of interchain interactions
anhydrides, and compounds containing carboxy groups compared to polydiene urethane epoxides [18]. We also
[16]. Curing is performed, as a rule, at 70–90°С. believe that this approach should take into account the
For operation under the conditions of Extreme North, possibilities of an alternative pathway suggested in [19]
the materials should have high frost resistance, so as to for modification of materials: performing the synthesis
operate at temperatures down to –70°C. Compounds of epoxy-containing polymers under the conditions
based on oligodiene urethane epoxides exhibit allowing the content of diglycidyl urethane in them to be

1937
1938 STREL’NIKOV et al.

increased. On the other hand, the curing system used in in 5 h (see scheme). The content of free epoxy groups
[19] allows high mechanical characteristics of materials was determined according to GOST (State Standard)
to be reached only at a high curing temperature (90°С), 12497–78.
which restricts the applicability of this modification The synthesized oligomers were used for preparing
pathway to cold-curable binders. cured samples of polyurethane epoxides (PUEs) and
This study is aimed at improvement of EUO-based studying their physicomechanical and other functional
compounds for preparing effective frost-resistant binders properties. Two cycloaliphatic amines liquid at room
that can be used for the development of adhesives and temperature were used as curing agents: 3-aminomethyl-
protective paint-and-varnish coatings curable under 3,5,5-trimethylcyclohexylamine (isophorone diamine,
natural conditions of summer months at moderately cold IPDA) and aminoethylpiperazine (AEP); the latter
climate. amine contains primary, secondary, and tertiary nitrogen
atoms simultaneously.
EXPERIMENTAL Preliminarily we determined the base molar ratios
between EUO and amines in curing. They were chosen
Experiments were performed with a series of oligom- on the basis of the previous data [18, 20] and were as
ers of urethane diepoxide type, synthesized from ure- follows: EUO : amine = 1 : 0.87 with AEP and 1 : 0.75
thane-containing oligoether diisocyanates: prepolymers with IPDA.
(PPs) and pseudoprepolymers (PPPs) with terminal
To perform curing, EUO was stirred with the
functional isocyanate groups [oligo(tetramethylene ox- amine for 5 min in a vacuum (1–2 kPa) at 25 ± 1°С.
ide) diisocyanates] and glycidol. The prepolymers and The resulting mixture was kept for 24 h at 25 ± 1°С in
pseudoprepolymers were prepared from an polytetra- slit-type metal molds. The curing time was determined
methyleneoxide diol (PTMO), molecular mass ≈1400) in preliminary experiments as the time ensuring
and 2,4-toluene diisocyanate (TDI) (see Scheme). The complete conversion of epoxy groups in accordance
molar ratio of NCO and OH groups in the synthesis with the Fourier-transform IR spectra (disappearance
was from 2.03 to 4.03. At the ratio of 2–2.03, the final of the absorption band at 910 cm–1 [21–23]). The
product is the true prepolymer; at higher ratios, the final softening point of the hard phase, Тn, was determined
product (pseudoprepolymer) is a mixture of the prepoly- by thermomechanical analysis with a TMA/SDTA 841e
mer and initial diisocyanate. device (Mettler Toledo) at a scanning rate of 0.05 deg
PTMO was preliminarily dried with stirring at s–1 under a load of 0.015 MPa. The glass transition point
80°С and residual pressure of 1–2 kPa. The first step Тgs was determined by differential scanning calorimetry
of the synthesis was performed in a sealed laboratory (DSC) with a DSC 822е calorimeter (Mettler Toledo) at
mixer equipped with a heating jacket. After loading a scanning rate of 0.08 deg s–1.
the components, the temperature was kept at 60°С for Mechanical tests of the samples were performed
1 h, elevated to 80°С, and kept on this level for 6 h with an INSTRON 3365 universal testing machine at
with stirring. The reaction was performed to attain 25 ± 1 and –70 ± 1°С in accordance with ISO 37–2013.
the constant content of isocyanate groups, which was We determined the nominal strength σk (maximal stress
determined by back-titration with n-butylamine in calculated per initial cross section of the specimen),
accordance with ASTM D2572-080. relative critical strain εk (%), and nominal modulus Е100
In the second step, the PPs and PPPs obtained were (stress at relative strain ε = 100%). The pull strength
treated with glycidol at the OH : NCO molar ratio of σpull of elastomer–steel adhesive joints was determined
2 : 1. A catalyst, dibutyltin dilaurate (DBTDL), was according to GOST 14760–69 using mushroom-shaped
added to the reaction mixture in an amount of 0.03 specimens at a polymer layer thickness of 2 ± 0.1 mm,
wt % relative to the total mixture weight to accelerate and the shear strength σshear of adhesive joints with
the process. This step was performed at 70°С in the aluminum of AD0 grade, according to GOST 14759–69.
above mixer. The completeness of the conversion of The variation of the viscosity in the course of curing
NCO groups was monitored by Fourier-transform IR of urethane–epoxy compounds was studied with a
spectroscopy (disappearance of the absorption band at Rheotest 2.1 rotary viscometer (Germany) with the
2270 cm–1). The EUO synthesis was virtually complete cone–plate working unit at 25 ± 1°C and a shear rate

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 PREPARATION AND PROPERTIES OF FROST-RESISTANT MATERIALS 1939

Scheme. EUO synthesis.

of 180 s–1 [24]. From the results of rheological tests, this case the glass transition point of a polymer matrix,
we constructed the kinetic curves η(t) characterizing i.e., the glass transition point of soft blocks, will depend
the variation of the dynamic viscosity of the reaction on the concentration of DGU fragments in the polymer
mixture in time. chain to a considerably lesser extent. On the other hand,
we can hope that the presence of fragments of relatively
RESULTS AND DISCUSSION hard structure in the chain will improve the elastic and
strength properties of the cured materials.
The characteristics of the EUOs synthesized from Figure 1 shows the DSC curves of the synthesized
oligodiisocyanates via epoxidized oligomers are given viscous liquid EUOs. As can be seen, with an increase
in Table 1. The theoretical content of functional groups
was calculated from the molar ratios of the monomers DSC
and their molecular masses.
The specific feature of the second step of the EUO
synthesis is that, when using pseudoprepolymers,
the oligomeric epoxy urethane can be formed not
as a single product but as a mixture with diglycidyl
urethane (DGU), a product of the reaction of glycidol
with diisocyanate. The formation of such mixtures of
monomers with oligomeric products of essentially
different structure often leads to microphase segregation exo
in the curing step; as a result, the final polymers exhibit
two glass transition points. Such effect is typical, e.g., of
segmented polyurethanes [25]. T, °C
We believe that such microphase segregation can be a
favorable factor in the formation of an optimum structure Fig. 1. DSC curves of (1) EUO-1, (2) EUO-2, (3) EUO-
of frost-resistant compounds based on EUO, because in 3, (4) EUO-4, and (5) EUO-5.

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1940 STREL’NIKOV et al.

Table 1. Characteristics of EUOs

Content of free functional groups in the oligomer, %
NCO : OH molar ratio
Oligodiisocyanate isocyanate (in
EUO in oligodiisocyanate epoxy (in EUO)
in EUO synthesis oligodiisocyanate)
synthesis
calculated actual calculated actual

EUO-1 PP-1 2.03 4.79 4.75 4.52 4.23

EUO-2 PPP-2 2.43 6.56 6.49 5.71 5.27
EUO-3 PPP-3 2.73 7.72 7.62 6.56 6.39
EUO-4 PPP-4 3.03 8.81 8.92 7.87 8.03
EUO-5 PPP-5 4.03 12.07 12.22 10.28 10.41

in the DGU fraction in the mixture the glass transition were assigned using the results of spectroscopic studies
point of the soft matrix regularly increases, which is of structurally related polymers with urethane groups
caused by a decrease in the mobility of elastic chains due [26, 27]. PUE-1 and PUE-6 synthesized without excess
to formation of additional hydrogen bonds. The melting diglycidyl urethane exhibit absorption bands at 1702 cm–
peak at 20°C, corresponding to the phase transition of 1, belonging to the vibrations of carbonyl hydrogen-
hard blocks containing DGU fragment, appears in all bonded with the N–H group of the urethane hydroxyl
the curves. The intensity of this transition regularly hard block (HB) (HB–HB bond), and at 1730 cm–1,
increases with an increase in the diglycidyl urethane belonging to the vibrations of the free urethane carbonyl
content. group [18]. It should be noted that the intensity of the
Analysis of the FTIR spectra in the range of carbonyl peak at 1730 cm–1 for PUE-1 sample is higher than for
stretching vibrations (wavenumber interval ν = 1600– PUE-6 sample (cured with IPDA), suggesting higher
1760 cm–1) revealed important features of the structural level of interchain interactions in polymers cured with
organization of PUE (Fig. 2). The absorption bands AEP. With an increase in the fraction of hard blocks
based on diglycidyl urethane, the intensity of the peaks
at 1702 and 1730 cm–1 regularly increases irrespective
of the curing agent.
Two glass transition points are clearly manifested
in the DSC curves (Figs. 3, 4) of cured elastomers
synthesized with excess DGU (elastomers without
excess DGU have a single glass transition point),
suggesting microheterogeneous structure of the
polymer. The glass transition point of the soft polymer
matrix does not noticeably change with variation of the
DGU concentration. The formation of hard blocks in
the polymer matrix upon DGU curing, corresponding
to the appearance of nanodispersed high-modulus filler,
significantly increases the nominal modulus, hardness,
and strength of the cured material (Table 2).
As seen from Fig. 5, in all the cases chemical
ν, cm–1 transformations start immediately after mixing the
components without induction period. Despite the fact
that the viscosity variation follows different laws, as
Fig. 2. Fragment of the IR spectra of (1) PUE-1, (2) PUE- indicated by the shape of the kinetic curves, correlation
4, (3) PUE-5, (4) PUE-6, (5) PUE-9, and (6) PUE-10. is observed between the gelation rate and DGU amount

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 PREPARATION AND PROPERTIES OF FROST-RESISTANT MATERIALS 1941

DSC DSC

exo

exo

T, °C T, °C

Fig. 3. DSC curves of (1) PUE-1, (2) PUE-2, (3) PUE- Fig. 4. DSC curves of (1) PUE-6, (2) PUE-7, (3) PUE-8,
3, (4) PUE-4, and (5) PUE-5. (4) PUE-9, and (5) PUE-10.

dimensional cross-linked structures accelerate [28]. The in the initial reaction mixture. The larger is the DGU
process leads to the formation of not only chemical but amount in the initial oligomer, the higher is the curing
also physical network as a result of phase segregation of rate of the compound based on this EUO; i.e., the
hard and soft blocks [29] and intermolecular interactions, chemical reactions responsible for the formation of three-

Table 2. Main characteristics of cured compounds based on EUOs

DGU Adhesion
mole strength, MPa Shore
Curing σk, εk, Е100,
Sample EUO used fraction in Т, °С
MPa MPa Тn, °С hardness A,
agent %
mixture units
with EUO σpull σshear

PUE-1 EUO-1 AEP 0 25 8.9 491 1.8 4.2 3.2 143 73

–70 48.5 7 – – –
PUE-2 EUO-2 0.29 25 12.9 344 5.3 6.8 4.2 145 87
–70 52.0 14 – – –
PUE-3 EUO-3 0.41 25 13.8 295 6.9 7.5 5.4 151 93
–70 54.0 8 – – –
PUE-4 EUO-4 0.50 25 15.3 256 9.1 8.1 7.1 154 95
–70 55.8 10 – – –
PUE-5 EUO-5 0.66 25 18.6 123 18.4 8.5 7.6 157 98
–70 53.8 20 – – –
PUE-6 EUO-1 IPDA 0 25 7.2 516 1.2 4.5 3.6 145 82
–70 45.4 7 – – –
PUE-7 EUO-2 0.29 25 15.9 218 7.4 7.3 5.6 150 91
–70 56.8 10 – – –
PUE-8 EUO-3 0.41 25 17.8 215 8.6 9.0 7.4 152 96
–70 55.8 9 – – –
PUE-9 EUO-4 0.50 25 27.2 211 12.9 12.8 8.6 155 99
–70 60.4 9 – – –
PUE-10 EUO-5 0.66 25 24.1 171 22.4 11.3 8.2 156 100
–70 79.2 12 – – –

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1942 STREL’NIKOV et al.

η, Pa s
(a)

σ, MPa
t, min
(b)

σ, MPa
Fig. 5. Dynamic viscosity growth curves for (1) PUE-
6, (2) PUE-1, (3) PUE-9, (4) PUE-4, (5) PUE-10, and
(6) PUE-5.

which, in turn, is accompanied by a sharp increase in the

viscosity.
The maximal rate of the viscosity growth is observed
for EUO-based systems synthesized with a fourfold
excess of TDI: PUE-5 (curve 5) and PUE-10 (curve 6).
The kind of the curing agent does not significantly
influence the gelation rate in this case, influencing
only the initial viscosity η0, which for PUE-5 is almost
1.5 times higher than η0 of PUE-10. For EUO-based
compounds synthesized with a two- or threefold
excess of TDI, the influence of the kind of the curing
agent is more pronounced. Whereas the viscosity of Fig. 6. Stress–strain curves at 25°С for samples
compounds cured with AEP varies in accordance with (a) PUE-1–PUE-5 and (b) PUE-6–PUE-10 (curves
an approximately exponential law (curves 2 and 4), the 1–10, respectively).
EUOs cured with IPDA are characterized by significant
deceleration of the gelation (curves 1 and 3). by more pronounced strengthening with an increase in
It is known that the curing rate significantly influ- the fraction of DGU in a mixture with EUO. We attribute
ences the formation of the regular structure and the this fact to the formation of different structures of the
physicomechanical characteristics of urethane-contain- hard PUE phase when using different curing agents.
ing low-temperature-curable composites [30]. Compari- For example, Ahn et al. [31] have shown that the hard
son of the results of rheological and physicomechanical phase structure formed when using isophorone diamine
studies (Table 2; Figs. 6a, 6b) shows that, the higher is as an agent extending the chain of urethane-containing
the DGU content in a mixture with EUO, the more rapid elastomers is loose and poorly ordered. The formation of
is the viscosity growth. the loose hard phase is due to the bulky structure of the
The presence of a tertiary nitrogen atom in AEP diamine, preventing the formation of a regular structure.
makes its more reactive, compared to IPDA, in EUO The loose structure favors the energy dissipation due to
curing. The materials cured with IPDA are characterized disintegration of coarse hard blocks into finer blocks,

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 PREPARATION AND PROPERTIES OF FROST-RESISTANT MATERIALS 1943

leading to enhancement of the tensile strength of the diisocyanate were taken in 1 : (2.03–4.03) ratio. The use
material. This is indeed observed in the experiment: The of cycloaliphatic amines for curing the oligomers ob-
stress–strain curves for the IPDA-cured PUE samples tained allows using the “cold” curing conditions, i.e.,
demonstrate strengthening of the material in the last step curing at temperatures close to 20–25°С.
of the extension, whereas the AEP-cured PUE samples (2) The use of conditions favoring the formation of
do not exhibit such effect. Similar effects were observed diglycidyl urethane fragments in synthesis of epoxy
previously when using isophorone diisocyanate in the urethane oligomers leads to sharp enhancement of the
synthesis of poly(urethane ureas) [32]. strength and adhesion of the cured materials.
The results of the mechanical tests (Table 2) (3) The use of isophoronediamine for curing
show that the nominal strength, nominal modulus, epoxy urethane oligomers favors more pronounced
and adhesion characteristics of the material at room strengthening of the material upon introduction of
temperature appreciably increase with an increase in diglycidyl urethane fragments, compared to curing with
the DGU content in a mixture with EUO, whereas the aminoethylpiperazine. This is caused by the formation
relative critical strain regularly decreases. In the IPDA- of the loose structure of the hard phase in curing with
cured materials, the strengthening effect observed with isophoronediamine.
an increase in the DGU fraction in the mixture is more (4) The presence of diglycidyl urethane fragments
pronounced. At the DGU mole fraction in the mixture in the polymer chain of epoxy urethane oligomers
х2 = 0.5 (PUE-5), the nominal strength upon curing with based on oligotetrahydrofuran does not significantly
AEP increases by a factor of 2.1, from 8.9 (PUE-1) to influence the glass transition point of the elastic phase
18.6 MPa (PUE-5), the pull strength of the adhesive of the cured polymer materials. This fact, accounted
joint with steel increases by a factor of 2.02, from 4.2 for by the microphase segregation of the materials,
to 8.5 MPa, and the shear strength of the adhesive joint makes promising the development of high-strength low-
with aluminum increases by a factor of 2.4, from 3.2 glass-transition-point polymer matrices based on the
to 7.6 MPa. In curing with IPDA, the maximal strength oligomers studied.
is reached at the DGU mole fraction in the mixture
х2 = 0.50: the nominal strength upon curing increases ACKNOWLEDGMENTS
by a factor of 3.7, from 7.1 (PUE-6) to 27.2 MPa (PUE-
9), the pull strength of the adhesive joint with steel The study was financially supported by the Ministry
increases by a factor of 2.8, from 4.5 to 12.8 MPa, and of Education and Science of the Russian Federation
the shear strength of the adhesive joint with aluminum (agreement no. 14.604.21.0192, unique project identifier
increases by a factor of 2.4, from 3.6 to 8.6 MPa. RFMEFI60417X0192).
At negative temperatures, the strengthening effect is
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