1070-4272/02/7502-0261 $27.00 C 2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 2, 2002, pp. 261!264. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 2, 2002,
Original Russian Text Copyright + 2002 by Russavskaya, Silinskaya, Yakimova, Korchevin, Tomin, Deryagina.
AND INDUSTRIAL ORGANIC CHEMISTRY
Thiokols Based on Wastes from Epichlorohydrin
Production as Components of Rail Lubricants
N. V. Russavskaya, Ya. N. Silinskaya, G. A. Yakimova, N. A. Korchevin,
V. P. Tomin, and E. N. Deryagina
Favorskii Institute of Chemistry, Irkutsk, Russia
Received September 27, 2001
Abstract-Preparation of solid polymers with varied content of sulfur by condensation of 1,2,3-trichloro-
propane-rich wastes from epichlorohydrin production with sodium polysulfide Na
(x =134) generated by
reductive dissolution of sulfur in the hydrazine hydrate3alkali system was studied.
Various organosulfur compounds are used as anti-
wear and extreme-pressure additives to lubricants
[1, 2]. In contrast to other lubricants, formulations
for rail lubrication at curved sections of railway lines
operate in rather specific conditions, because nonsta-
tionary friction appearing at contact of the wheel
flange and the lateral surface of the rail head is char-
acterized by large specific loading and periodicity. At
this contact, the pressure and temperature increase for
short time , which can activate the molecules of
lubrication formulations and improve their sorption
on the rubbing elements. Therefore, sulfur and alkali
are added to some rail lubricants , because in the
presence of surfactants they sulfidize and strengthen
the wheel and rail surfaces. However, addition of
alkali and surfactants impairs other operation proper-
ties of lubricants and increases their corrosion activity
and environmental hazard.
Sulfur-containing polymers (thiokols) based on
wastes from epichlorohydrin production are often used
as additives to rail lubricants.
In industry, thiokols are prepared from dihalo de-
rivatives [1,2-dichloroethane, di(>-chloroethyl) formal,
and dichlorodiethyl ether] and sodium polysulfide. To
obtain branched macromolecules, minor amounts of
1,2,3-trichloropropane (TCP) are often added [5!7].
As a rule, polymerization of the above components
yields rubbery or liquid polymers. Solid polymers,
prepared only in the presence of sodium monosulfide
S, contain low-reactive C!S groups, and their
use in lubrication formulations is rather difficult.
Rubbery polymers are immiscible with other lubricant
components, and liquid thiokols are mixed with them
only upon prolonged vigorous stirring.
At the same time, the source of raw materials for
thiokol production can be significantly expanded
owing to chlorine-containing wastes from industrial
organic synthesis. At present, utilization of these
wastes is a complex environmental problem [8, 9].
In this study, we prepared sulfur-containing poly-
mers from the wastes of epichlorohydrin production,
which is the main component of epoxy resins. In
industry, it is prepared from propylene in three stages
, and each stage is accompanied by various side
reactions. As a result, more than 500 kg of chlorine-
containing wastes are formed per 1000 kg of com-
mercial epichlorohydrin . These wastes are en-
riched in 1,2-dichloropropane, TCP, dichloropropan-
ols, or epichlorohydrin, depending on the sampling
point. Thus, specific compositions of the wastes,
which varies within a wide range, is determined by
the process conditions and operation stability of in-
The polysulfide polymers were prepared using
a TCP fraction containing (wt %): 76.6 TCP, 17.4 di-
chloropropanols, 2.0 1,2-dichloropropane, 2.1 dichlo-
ropropenes, and 1.9 other products.
The polymers can be prepared using two different
procedures for sodium polysulfide Na
In the first case (procedure 1), it was prepared by
a common procedure used in industrial production of