Kinetics and Mechanism of Ethylene Polymerization and Copolymerization Reactions with Heterogeneous Titanium-Based Ziegler-Natta Catalysts

  • Yury V. Kissin
  • Robert I. Mink
  • Thomas E. Nowlin
  • Anita J. Brandolini
Conference paper

Abstract

A detailed kinetic analysis of ethylene homopolymerization reactions and its copolymerization reactions with 1-hexene with a supported Ti-based Ziegler-Natta catalyst shows a number of kinetic features which are interpreted as a manifestation of multi-site catalysis. The catalyst contains several types of active centers which differ in stability and formation rates, the molecular weights of polymer molecules they produce and in their response to the presence of an α-olefin. Several kinetic effects in ethylene polymerization reactions require an introduction of a special kinetic mechanism which postulates an unusually low reactivity of the growing polymer chain containing one ethylene unit, the Ti-C2H5group. This peculiarity of the Ti-C2H5group, which is probably caused by its β-agostic stabilization, predicts two features of ethylene polymerization reactions which have not been described in the literature yet: (a) formation of deuterated ethylenes in ethylene homopolymerization reactions in the presence of deuterium, and (b) an apparently increased reactivity of α-olefins in chain initiation reactions involving the Ti-H bond. Both effects were confirmed experi-mentally.

Keywords

Polyethylene Oligomer Alkane Hydride Macromolecule 

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Copyright information

© Springer-Verlag Berlin Heidelberg 1999

Authors and Affiliations

  • Yury V. Kissin
    • 1
  • Robert I. Mink
    • 1
  • Thomas E. Nowlin
    • 1
  • Anita J. Brandolini
    • 1
  1. 1.Mobil Chemical Co.Edison Research Lab.EdisonUSA

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