Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

Rajeev Ananda Kumar, Priyadarsi De, Bin Zheng, Kuo-Wei Huang, Jack I. Emert, Rudolf Faust

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

The kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3·ether complexes in hexane at 0°C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR′FeCl4 - complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR′FeCl4 - ⇋ HCl + FeCl3·ROR′.
Original languageEnglish (US)
Pages (from-to)322-329
Number of pages8
JournalPolym. Chem.
Volume6
Issue number2
DOIs
StatePublished - 2015

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Biomedical Engineering
  • Bioengineering
  • Polymers and Plastics

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