Controlled/"living"radical polymerization of methyl methacrylate catalyzed by benzyl chloride/iron dichloride tetrahydrate/triphenyl phosphine

Controlled/"living" radical polymerization of methyl methacrylate (MMA) initiated by benzyl chloride has been achieved by atom transfer radical polymerization (ATRP) catalyzed by iron dichloride tetrahydrate/triphenyl phosphine complexes at 90 C. When the amount of Fe to P is kept at 1: 2, the polymer number average molecular weight (M̄_n) increases linearly with conversion, and then the polymerization can be kept controlled and "living". If the amount of Fe to P is not kept at 1: 2, the linear relation of M̄_n to conversion does not exist, thus many active centers in the polymerization can form themselves. At the same time, methods of synthesis of iron-based catalysts have marked effects upon the ATRP of MMA.