Mechanism of photoinitiated radical polymerization of styrene in the presence of benzyldithiocarbamate iniferter

Abstract

The kinetics and mechanism of radical polymerization with participation of iniferter is studied using the styrene- S-benzyl- N, N-diethyldithiocarbamate system as an example. The identity of the photocomposition of S-benzyl- N, N-diethyldithiocarbamate and polystyrene macroiniferter is demonstrated by an ESR method, and the special features of the transformation of the molecular mass distribution during polymerization are revealed by means of GPC. It is shown that polymerization is characterized by the absence of bimolecular termination of the growing macroradicals and a stepped mechanism of the chain propagation reaction. The experimental data are in good agreement with our previously proposed general kinetic scheme for radical polymerization with the participation of iniferter.