Radical polymerization of methyl methacrylate with methyl 2,2-dimethyl-3,3-diphenyl-3-cyanopropionate as a thermal iniferter

Summary To clarify the mechanism of living radical polymerization of methyl methacrylate (MMA) with tetraphenylsuccinodinitrile (TPSN) as a thermal iniferter, a model compound for the end group of the poly(MMA) produced, methyl 2,2-dimethyl-3,3-diphenyl-3-cyanopropionate (2), was synthesized and found to initiate a living radical polymerization of MMA, indicating that the hexa-substituted C-C bond in 2 dissociated into radicals. The poly(MMA) thus obtained further initiated the radical polymerization of styrene (St) to give a block copolymer.