New insight into the polymerization mechanism of 1,3-dienes cationic polymerization. IV. Mechanism of unsaturation loss in the polymerization of isoprene
PERUCH, Frédéric
Laboratoire de Chimie des Polymères Organiques [LCPO]
Team 1 LCPO : Polymerization Catalyses & Engineering
< Leer menos
Laboratoire de Chimie des Polymères Organiques [LCPO]
Team 1 LCPO : Polymerization Catalyses & Engineering
Idioma
en
Article de revue
Este ítem está publicado en
Polymer Chemistry. 2017, vol. 8, n° 5, p. 926-935
Royal Society of Chemistry - RSC
Resumen en inglés
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 ...Leer más >
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.< Leer menos
Palabras clave en inglés
Isoprene
Breaking process
Chain transfer
First order kinetics
Multiple interactions
Number average
Polymer chains
Polymerization mechanisms
Branched structures
Cationic polymerization
Orígen
Importado de HalCentros de investigación