ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 11, pp. 1820−1826. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.A. Rozentsvet, V.G. Kozlov, N.A. Korovina, O.A. Stotskaya, I.A. Pronina, L.V. Agibalova, E.Yu. Maretina, 2015, published in Zhurnal
Prikladnoi Khimii, 2015, Vol. 88, No. 11, pp. 1606−1612.
AND POLYMERIC MATERIALS
Synthesis of SKOP Oligopiperylene Rubber
on Vanadium Catalytic Systems
V. A. Rozentsvet
, V. G. Kozlov
, N. A. Korovina
, O. A. Stotskaya
, I. A. Pronina
L. V. Agibalova
, and E. Yu. Maretina
Institute of Volga Basin Ecology, Russian Academy of Sciences, ul. Komzina 10, Togliatti, Samara oblast, 445003 Russia
Lebedev Research Institute of Synthetic Rubber, Gapsal’skaya ul. 1, St. Petersburg, 198035 Russia
Received August 11, 2015
Abstract—Speciﬁ c features of cationic polymerization of 1,3-pentadiene under the action of modiﬁ ed catalytic
systems based on vanadium oxytrichloride were studied. The most effective agents controlling the molecular
characteristics in synthesis of poly-1,3-pentadiene on vanadium catalysts are tert-butyl chloride and a combination
of tert-butyl chloride with diisopropyl ether. The suggested catalytic systems allow virtually complete conversion
of the monomer to be reached within a technologically acceptable time. The developed vanadium catalytic systems
are recommended for commercial production of Oligopiperylene Rubber SKOP.
Cationic polymerization is widely used in industry for
the synthesis of polymers exhibiting unique structure of
the macromolecular chain and high physicomechanical
characteristics. Important advantages of this method
are relatively low cost of catalytic systems, high
polymerization rates, and possibility of involving in the
process monomers capable of polymerization by the
cationic mechanism only .
It is known that piperylene (1,3-pentadiene)
polymers can be prepared using various polymerization
methods, but only cationic polymerization of this
monomer ensures high polymerization rate and the
possibility of reaching complete conversion of the
monomer within a technologically acceptable time
[2, 3]. 1,3-Pentadiene is used in Russia in commercial
production of Oligopiperylene Rubber SKOP.
The production process is based on the cationic
polymerization of 1,3-pentadiene under the action
of the TiCl
O catalytic system . This catalytic
system has a number of signiﬁ cant drawbacks.
The 1,3-pentadiene polymerization rate is largely
determined by the water content of the reaction mixture,
and even slight ﬂ uctuations of the water concentration
in the system lead to a sharp change in the process rate
and to overheating of the reaction mixture .
Catalytic systems based on various Lewis acids
such as AlCl
[3, 10], and ZnBr
 for cationic polymerization of
1,3-pentadiene have been described in the literature.
The known catalytic systems, though effecting the
1,3-pentadiene polymerization, have certain drawbacks
and are not used in SKOP rubber production.
Previously  we demonstrated the principal pos-
sibility of the cationic polymerization of 1,3-pentadiene
under the action of vanadium oxytrichloride. Although
vanadium catalytic systems have certain indubitable
advantages, their signiﬁ cant drawback is high probabil-
ity of the formation of an insoluble fraction (IF) in the
product in the course of 1,3-pentadiene polymerization.
Furthermore, the polymerization occurs in essentially
nonstationary mode, which does not allow reaching
high monomer conversion.
The aim of this study is search for new VOCl
based catalytic systems allowing the IF formation to be
excluded, the molecular characteristics of the forming
poly-1,3-pentadiene to be controlled, and practically