ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 12, pp. 2093!2096. C Pleiades Publishing, Ltd., 2007.
Original Russian Text C A.Ya. Samuilov, E.I. Galeeva, A.V. Kulikov, I.N. Bakirova, Ya.D. Samuilov, 2007, published in Zhurnal Prikladnoi Khimii,
2007, Vol. 80, No. 12, pp. 2015!2018.
AND INDUSTRIAL ORGANIC CHEMISTRY
A. Ya. Samuilov, E. I. Galeeva, A. V. Kulikov,
I. N. Bakirova, and Ya. D. Samuilov
Kazan State Technological University, Kazan, Tatarstan, Russia
Received March 23, 2007
Abstract-Sulfur-containing oligoethers were prepared by polycondensation of thiodiglycol in the presence
of acid catalysts. These oligoethers are oligomers with terminal hydroxy groups, comprised of oxyalkyl
Development of oil- and gas-resistant materials is
an urgent task faced by modern polymer chemistry.
One of the ways to accomplish this task consists in
incorporation of sulfur atoms into the polymer matrix.
For example, vulcanizates of Thiokols are well known
to be resistant to fuels and oils . Their large-scale
production is hindered, however, by imperfect tech-
nology of production of polysulfide oligomers, yield-
ing abundant wastewater. Wastewater utilization en-
tails large costs, which increases the price of Thiokols.
Also, materials based on polysulfide oligomers have
poor strength characteristics. A high strength is ex-
hibited by SKU-PFL commercial polyurethane based
on oligo(oxytetramethylene) glycol (OOTMG). This
is currently the most demanded castable polyurethane,
but its oil and gas resistance is low.
In this context, it was of interest to replace OOTMG
in synthesis of SKU-PFL polyurethane with a sulfur-
containing oligoether diol and compare the properties
of the new material with those of the OOTMG-based
material. It could be expected that the new material
would combine the properties of Thiokols and poly-
As the initial compound for preparation of the olig-
oether with sulfur atoms in the backbone served thio-
diglycol (TDG) synthesized by the reaction between
ethylene chlorohydrin and sodium sulfide [2, 3]:
3Cl + Na
Oligothiodiglycols (OTDGs) with a molecular
weight of 80031200 were prepared by TDG polycon-
H+(n 3 1)H
For synthesis, we used both [crude] TDG (TDG-C)
and that freed from impurities by distillation.
The process was run at 1103115oC in a toluene
medium with azeotropic distillation of water; sulfuric
acid served as the catalyst.
The content of the hydroxy groups in the oligo-
ethers was determined by acetylation with acetic
anhydride in the presence of pyridine according to
GOST (State Standard) 252361. The concentration of
isocyanate groups was determined by the [amine
equivalent] method . The IR spectra were recorded
for oligoether films on a PE FTIR 1720 Perkin3
Elmer (UK) spectrophotometer, and the
tra, in a perdeuteroacetonitrile solution on a Bruker
MSL-400 (Germany) device at 400 MHz.
Quantum chemical calculations were carried out by
B3LYP ab initio hybrid method in the STO 3-21G
basis set with the use of the GAUSSIAN 03 software
package . The calculations involved full optimiza-
tion of the configuration of the compounds. The initial
optimization of the configuration was carried out by
RM3 semiempirical method, and the resulting data
were used for further calculations.
Polyurethanes were prepared via synthesis of
a prepolymer by the reaction between OOTMG or