Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 6, pp. 974−979.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.R. Bazhenova, E.A. Glukhov, A.G. Mustaﬁ n, Yu.B. Monakov, 2012, pblished in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 6,
AND POLYMERIC MATERIALS
Inﬂ uence of the Structure of the Organoaluminum
Compound on the Stereoregulating Heterogeneity
of Catalytic Systems Based on TiCl
I. R. Bazhenova, E. A. Glukhov, A. G. Mustaﬁ n, and Yu. B. Monakov
Institute of Organic Chemistry, Ufa Scientiﬁ c Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Institute of Oil-and-Gas Technologies and New Materials, Academy of Sciences of Bashkortostan Republic,
Ufa, Bashkortostan, Russia
Received May 27, 2011
Abstract—The stereoregulating heterogeneity manifested in butadiene polymerization by active sites of the tita-
nium catalytic system formed “separately” in combination with organoaluminum ligands was examined.
The development of macromolecular chemistry is
intimately associated with the possibilities of controlling
the formation of the polymer microstructure .
Recently much attention has been given to the multiple-
site nature of ion-coordination catalytic systems and
to its dependence on such factors as catalytic system
composition and conditions of the polymerization and
catalyst preparation [2, 3]. Studies in the ﬁ eld of the
multiple-site nature [4, 5] showed that the polymerization
sites are heterogeneous not only in the kinetic activity,
but also in stereospeciﬁ city of the action.
The stereoregulating heterogeneity of titanium-
containing catalytic systems in butadiene polymerization
leads to the formation of structural isomers strongly
differing in the physicochemical properties (1,4-cis,
1,4-trans, 1,2 units) and determines their distribution in
The most convenient reaction for studying the
stereoregulating heterogeneity of catalytic systems is
polymerization of dienes with the formation of polymers
of mixed microstructure. According to some data,
mixed microstructure of the polymer may be due to the
fact that the ﬁ nal product is a mechanical mixture of the
polymers. For example, separation of the product of the
butadiene polymerization on TiCl
1.3) by extraction with various solvents allowed isolation
of highly stereoregular 1,4-trans-polybutadiene from
the mixture of the products . Studies of samples of
crystalline polybutadiene with a high content of 1,4-cis
structures , obtained using various catalysts, showed
that, despite similar composition of the rubbers with
respect to stereoregularity, their melting points differ.
This is due to the presence of blocks of cis isomers.
Sigaeva et al. [4, 5] showed previously that, in
polymerization of butadiene in situ under the action of the
catalytic system TiCl
under the conditions
corresponding to the maximal activity of the catalyst,
formation of polybutadiene of mixed microstructure is
possible as a result of formation of three types of active
sites, differing in the stereoregulating power. Sigaeva et
al. note the relationship between the molecular weight
and microstructure for all the isolated polybutadiene
fractions. However, data on how the procedure for
forming the catalytic system and the structure of the
organoaluminum compound affect the stereoregulating
heterogeneity of active sites of ion-coordination systems
in butadiene polymerization are lacking.
The goal of this study was to determine the
stereoregulating heterogeneity of active sites of the
titanium catalytic system in combination with AlCl(i-