Jump to main content
Jump to site search

Issue 5, 2017
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 05 Oct 2016, accepted on 21 Dec 2016 and first published on 21 Dec 2016


Article type: Paper
DOI: 10.1039/C6PY01736C
Citation: Polym. Chem., 2017,8, 926-935

  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements