Radical polymerization of acrylonitrile initiated by α‐picolinium p‐chlorophenacylid

Abstract

The radical polymerization of acrylonitrile (AN) with a-picolinium pchlorophenacylid (a-PCPY) as initiator using carbon tetrachloride as inert solvent was investigated at 50°C. The polymerization follows ideal kinetics : the exponent values calculated for the initiator and monomer were found to be 0.5 and unity, respectively. A free radical mechanism with bimolecular termination was confirmed by the inhibiting effect of hydroquinone, a radical quencher. The rate of polymerization was a direct function of initiator (a-PCPY) concentration, monomer (AN) concentration and temperature. The overall activation energy calculated was 56 kJ/mol. The polymerization was favoured by polar solvents and retarded by non-polar solvents. K e y words: acrylonitrile, nitrogen-ylid, kinetics, polymerization.