Effects of phosphorous oxychloride,phosphorous trichloride and dichlorophenylphosphine on the radical polymerisation of acrylonitrile under heterogeneous conditions

Summary The effects of C₆H₅PCl₂, POCl₃, and PCl₃ on the free radical polymerisation of acrylonitrile initiated bya,a-azobisisobutyronitrile were kinetically investigated in benzene and trichloroethylene solutions. With PCl₃ rates of polymerisation were unaffected but the degrees of polymerisation were found to decrease with increasing PCl₃. With C₆H₅PCl₂ and POCl₃ however both rates and degrees of polymerisation were adversely affected. Thus PCl₃ acts as a chain transfer agent while the other two phosphorous compounds function as degradative chain transfer agents.