LIVING CHARACTER OF THE POLYMERIZATION OF BUTYL ACRYLATE INITIATED BY A MODEL N,N-DIETHYLDITHIOCARBAMATE

The polymerization of n-butyl acrylate has been initiated, in toluene solution at 30 degrees C, by photolysis of n-butyl-2-(N,N-diethyl dithiocarbamyl) propionate, which is a model of terminal groups end-capped by dithiocarbamate. The ratio of initiation to propagation rates is low, but the polymers have approximately the theoretical <(DP)over bar>n. Initiation with a functionalized polybutyl acrylate shows that reactivation of the end-groups takes place at the same rate as with an equivalent concentration of initiator. The reaction scheme assumes reversible termination by reactivation of the dithiocarbamyl end-groups and non reversible terminations such as combination of the growing chains and degradative chain transfer (with formation of tetraethylthiuram disulfide). It has been shown that the functionalizing reversible termination is predominant.