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Issue 5, 2017
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New insight into the polymerization mechanism of 1,3-dienes cationic polymerization. IV. Mechanism of unsaturation loss in the polymerization of isoprene

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Abstract

The cationic polymerization of isoprene with the tBuCl/TiCl4 initiating system in the presence of a high excess of tBuCl over TiCl4 ([tBuCl]/[TiCl4] > 100) in CH2Cl2 is reported. It is shown that the polymerization follows first-order kinetics, which indicates that the main chain-breaking process is the chain transfer to the initiator. The number-average functionalities with respect to the tert-butyl head group and chlorine-containing end group are determined to be considerably higher than unity. In addition, unsaturation of the polymer chain is found to be always less than 100%. It is also shown that unsaturation of the polyisoprene chain decreases with a simultaneous increase in polydispersity upon treatment of the polymer using the tBuCl/TiCl4 initiating system. Based on these observations, the mechanism to obtain a polymer with reduced unsaturation is proposed, which includes multiple interactions of growing cations with double bonds of “own” or/and “alien” macromolecules with the formation of branched structures.

Graphical abstract: New insight into the polymerization mechanism of 1,3-dienes cationic polymerization. IV. Mechanism of unsaturation loss in the polymerization of isoprene

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Article information


Submitted
05 Oct 2016
Accepted
21 Dec 2016
First published
21 Dec 2016

Polym. Chem., 2017,8, 926-935
Article type
Paper

New insight into the polymerization mechanism of 1,3-dienes cationic polymerization. IV. Mechanism of unsaturation loss in the polymerization of isoprene

V. A. Rozentsvet, V. G. Kozlov, N. A. Sablina, O. A. Stotskaya, F. Peruch and S. V. Kostjuk, Polym. Chem., 2017, 8, 926
DOI: 10.1039/C6PY01736C

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