Cationic olefin polymerization using alkyl halide alkylaluminium initiator systems

II. Molecular weight studies
  • Joseph P. Kennedy
  • Prakash D. Trivedi
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 28)


The effect of t-BuX, Et2AlX and EtAlCl2, MeX and temperature on PIB molecular weight has been studied by GPC and viscometry. A large amount of \(\overline M _{\text{n}} , \overline M _{\text{w}}\), MWD as well as \(\overline M _{\text{v}}\) and \(\Delta E_{\overline {\text{M}} _{\text{v}} }\) (activation energy of viscosity average molecular weight) data were generated. Influence of monomer concentration on \(\overline M _{\text{n}}\) and \(\overline M _{\text{v}}\) was analyzed by Mayo plots and relative rate constants were calculated. Predominant molecular weight controlling mechanisms in t-BuCl and t-BuBr/Et2AlCl/MeCl systems were determined.

A relation between \(\Delta E_{\overline {\text{M}} _{\text{v}} }\) and molecular weight controlling mechanisms was discovered and the effect of initiator system, solvent and temperature on \(\Delta E_{\overline {\text{M}} _{\text{v}} }\) was explained. The present work has led to an understanding of the effect of counteranion on PIB molecular weight. These studies provide better insight into the detailed mechanism of isobutylene polymerization, in particular into the initiation and the molecular weight controlling events.


Molecular Weight Distribution Monomer Concentration Initiator System Total Polymer Relative Rate Constant 
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Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • Joseph P. Kennedy
    • 1
  • Prakash D. Trivedi
    • 1
  1. 1.Institute of Polymer ScienceThe University of AkronAkronUSA

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