Adv Polym Sci (2013) 257: 99–134
DOI: 10.1007/12_2013_227
© Springer-Verlag Berlin Heidelberg 2013
Published online: 14 July 2013
Kinetics of Olefin Polymerization and Active
Sites of Heterogeneous Ziegler–Natta
Catalysts
Lyudmila A. Novokshonova and Vladimir A. Zakharov
Abstract Kinetic investigations of olefin polymerization with Ziegler–Natta (ZN)
catalysts provide information for understanding the mechanism of these reactions
and are also necessary for development of industrial productions of polyolefins. In
this chapter, the main kinetic features of olefin polymerization with heterogeneous
ZN catalysts are considered as well as problems such as a deviation from the linear
dependence of the rate of polymerization on monomer concentration, the hydrogen
effect in ethene and propene polymerizations, and the comonomer effect, the
natures of which are not yet completely clear and are discussed in the literature.
For analysis of the kinetics and mechanism of olefin polymerization, data on the
number of active centers and propagation rate constants are important. The main
methods for determination of these kinetic parameters are discussed in this chapter.
Data on the number of active centers in ZN catalysts of different composition are
presented. On the base of these kinetic data, the hydrogen effect and the heterogeneity of active centers at propylene polymerization over ZN catalysts are analyzed.
Keywords Active site number Á Kinetic features Á Mechanism Á Metallorganic
catalysts Á Olefin polymerization
L.A. Novokshonova (*)
Semenov Institute of Chemical Physics, RAS, Moscow, Russia
e-mail: lnov@chph.ras.ru
V.A. Zakharov
Boreskov Institute of Catalysis, RAS, Novosibirsk, Russia
DOI: 10.1007/12_2013_227
© Springer-Verlag Berlin Heidelberg 2013
Published online: 14 July 2013
Kinetics of Olefin Polymerization and Active
Sites of Heterogeneous Ziegler–Natta
Catalysts
Lyudmila A. Novokshonova and Vladimir A. Zakharov
Abstract Kinetic investigations of olefin polymerization with Ziegler–Natta (ZN)
catalysts provide information for understanding the mechanism of these reactions
and are also necessary for development of industrial productions of polyolefins. In
this chapter, the main kinetic features of olefin polymerization with heterogeneous
ZN catalysts are considered as well as problems such as a deviation from the linear
dependence of the rate of polymerization on monomer concentration, the hydrogen
effect in ethene and propene polymerizations, and the comonomer effect, the
natures of which are not yet completely clear and are discussed in the literature.
For analysis of the kinetics and mechanism of olefin polymerization, data on the
number of active centers and propagation rate constants are important. The main
methods for determination of these kinetic parameters are discussed in this chapter.
Data on the number of active centers in ZN catalysts of different composition are
presented. On the base of these kinetic data, the hydrogen effect and the heterogeneity of active centers at propylene polymerization over ZN catalysts are analyzed.
Keywords Active site number Á Kinetic features Á Mechanism Á Metallorganic
catalysts Á Olefin polymerization
L.A. Novokshonova (*)
Semenov Institute of Chemical Physics, RAS, Moscow, Russia
e-mail: lnov@chph.ras.ru
V.A. Zakharov
Boreskov Institute of Catalysis, RAS, Novosibirsk, Russia