Reactivity of Z and E isomers, growing chain isomerization, and chain transfer reactions in ethene/2-butene copolymerization by metallocene-based catalysts

Pasquale Longo, Fabia Grisi, Gaetano Guerra, Luigi Cavallo

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

Copolymerization of Z and E isomers of 2-butene with ethene, in the presence of catalytic systems based on C2v-, Cs-, and C2-symmetric group 4 ansa-metallocenes is investigated. Higher reactivities of Z and E isomers of 2-butene, in the presence of C2- and Cs-symmetric metallocenes, respectively, are predicted by molecular modeling and are proved by polymerization tests relative to pure isomers as well as to mixtures of them. The copolymerization experiments have also shown that both growing chain isomerizations and chain transfer reactions are dependent on the configuration (Z or E) of 2-butene while are independent of the metallocene symmetry. To account for this behavior, isomerization mechanisms involving intermediates with metal-allyl bonds are suggested. Possible mechanisms of chain transfer reactions are also discussed.

Original languageEnglish (US)
Pages (from-to)4647-4659
Number of pages13
JournalMacromolecules
Volume33
Issue number13
DOIs
StatePublished - Jun 27 2000

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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