AND POLYMERIC MATERIALS
Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 6, pp. 988−994.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.G. Akhmetov, R.T. Burganov, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 6, pp. 1009−1016.
Polymerization of Butadiene under the Action
of Lithium Containing Initiating System
I. G. Akhmetov and R. T. Burganov
Public Corporation “Nizhnekamskneftekhim,” Nizhnekamsk, Tatarstan Republic, Russia
Received November 25, 2011
Abstract—Polymerization of butadiene under the action of n-butyl lithium modiﬁ ed by of alkali and alkaline
earth metal alkoxides was researched. Microstructure and molecular characteristics of the samples of polybuta-
diene synthesized were determined. The inﬂ uence of polymerization conditions on the properties of the resulting
polymer was examined.
The ﬁ rst manufacturer of polybutadiene with lithium
alkyls that has marketed large quantities of this polymer
is a ﬁ rm “Firestone” . Later, industrial plants for
manufacturing this type of rubber were put into operation
in Australia, Europe and Japan. Currently, this branch
continues to evolve, and the total production capacity
of anionic polybutadienes is more than 550 000 tons per
One of the major areas of butadiene rubber derived
from lithium alkyl is a modiﬁ cation of plastics to impart
strength toughness to composites [3–7]. The emergence
of new applications of plastics, such as pharmaceuticals,
medicine and food industry [8, 9], puts forward
a number of speciﬁ c requirements to polybutadienes:
preset microstructure and molecular characteristics,
lack of residual hydrocarbons and gel fraction, low
metal content and reduced coloration. So, investigations
of synthesis of polybutadienes with lithium-containing
catalysts are relevant also to the present time [10, 11].
The goal of the study is examination of the effect of
conditions occurring in butadiene polymerization under
the action of n-butyl lithium modiﬁ ed by alkali and
alkaline earth metal alkoxides on molecular parameters
and macrostructure of polybutadiene and, moreover,
computation of kinetic parameters of the process. The
results underlay designing butadiene rubber synthesis,
which has implemented in industry in Public Corporation
The monomer and solvent were processed according
to standard techniques of the anionic polymerization.
n-Butyl (n-BuLi) lithium was used as initiator. The
mixture of sodium and magnesium alkoxides (Scheme 1)
and magnesium–sodium alkoxide was as modiﬁ er (MD)
and it was granted by the Voronezh branch of FSUE
“NIISK” as a commercial product under the trade name
Lapramolat M-3 (TU 3840384-2007). Replacement of
sodium to potassium was carried out in a stage of the
modiﬁ er synthesis. The concentration of monomer was
1.3 mol L
. A mixture of n-hexane and toluene was
used as the solvent. For a more informative presentation
a modiﬁ er concentration in the reaction environment was
expressed as the molar ratio of MD : n-BuLi.
The polymerization was carried out in a steel reactor
with a stirrer (rotation speed 200 min
), jacket for
maintaining the required temperature, devices for input