Issue 2, 2015

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

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 [leftrightharpoons] HCl + FeCl3·ROR′.

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

Supplementary files

Article information

Article type
Paper
Submitted
28 Jul 2014
Accepted
11 Sep 2014
First published
12 Sep 2014

Polym. Chem., 2015,6, 322-329

Author version available

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

R. Kumar, P. De, B. Zheng, K. Huang, J. Emert and R. Faust, Polym. Chem., 2015, 6, 322 DOI: 10.1039/C4PY01039F

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