Thermal Self-Initiation in Stable Free-Radical Polymerization of Styrene

Stable free radical polymerization (SFRP) of styrene was carried out using bis(4-bromomethylbenzoyl)peroxide (BBMBPO)/4-hydroxyl-2,2,6,6-tetramethyl-1-piperidinyloxy (HTEMPO) or 4,4′-azobis(4-cyanopentyl)-α-bromoisobutyrate (ABCBIB)/HTEMPO as bimolecular initiating system. It was found that the molecular weights of obtained polystyrenes were controlled by the concentration of HTEMPO. Besides those generated by the initiators, some polystyrene chains were formed via thermal initiation. Polystyrene chains generated by the initiator had initiating groups for atom transfer radical polymerization (ATRP) at their ends, so they grew to higher molecular weights in ATRP of styrene. While the molecular weights of polystyrene chains generated by thermal initiation kept constant in ATRP conditions because of their inert terminals for ATRP. The amount of polystyrenes generated by thermal initiation was investigated quantitatively via gel permeation chromatography technique.