Block copolymers by combination of cationic and radical routes: 5. Polymerization of styrene initiated by 4,4′-azobis(4-cyanopentanoyl chloride)

The kinetics of the polymerization of styrene initiated by 4,4′-azobis(4-cyanopentanoyl chloride) (ACPC) was investigated in bulk and in benzene solution at 60°C. It was found that the overall rate of polymerization is proportional to the 0.48 power of the initiator concentration. The chain transfer-to-initiator and chain transfer-to-solvent constants were estimated to be C_I = 0.41 and C_S = 1.9 × 10^-4, respectively. Polymerization of styrene initiated by ACPC yields polystyrene with an acyl chloride terminal group at each end. Polymerization of tetrahydrofuran initiated by acyl chloride-terminated polystyrene in conjunction with AgSbF₆ provided the formation of a block copolymer.