The mechanism of the polymerization of n.butyl acrylate initiated with N, N-diethyl dithiocarbamate derivatives

Abstract

The kinetics of the photo-initiated polymerization of n.butyl acrylate by p-xylylene bis-( N, N-diethyldithiocarbamate) have been investigated in order to check the living character of this polymerization initiated with an “iniferter”. The reaction shows some features of a living system viz. growth of the molecular weight during the reaction under chosen conditions (high [M]/[I] ratios) and preparation of block copolymers. This confirms the existence of a reversible termination reaction between the growing chains and the dithiocarbamyl radicals. However, evidence has been found for the intervention of side reactions (formation of tetraethylthiuram disulphide, and decrease of the functionality of the polymers during the polymerization), indicating that the polymerization is not strictly living.