ROZENTSVET, Victor A.; KOZLOV, Valery G.; SABLINA, Nelly A.; STOTSKAYA, Olesya A.; PERUCH, Frédéric; KOSTJUK, Sergei V.

doi:10.1039/c6py01736c

Métadonnées

Afficher la notice complète

Licence d’utilisation du document

ROZENTSVET, Victor A.
Russian Acad Sci, Inst Ecol Volga River Basin

KOZLOV, Valery G.
Russian Acad Sci, Inst Ecol Volga River Basin

SABLINA, Nelly A.
Russian Acad Sci, Inst Ecol Volga River Basin

Langue

Article de revue

Ce document a été publié dans

Polymer Chemistry. 2017, vol. 8, n° 5, p. 926-935

Royal Society of Chemistry - RSC

Résumé en anglais

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.< Réduire

Mots clés en anglais

Isoprene

Breaking process

Chain transfer

First order kinetics

Multiple interactions

Number average

Polymer chains

Polymerization mechanisms

Branched structures

Cationic polymerization

Métadonnées

Partager cette publication !

Licence d’utilisation du document

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

Langue

Ce document a été publié dans

Résumé en anglais

Mots clés en anglais

URI

DOI

Origine

Unités de recherche