Radical polymerization of styrene and methyl methacrylate was investigated using a nickel-based initiating system

i．e．DCDPS／NiCl2／PPh3

in which diethyl 2

3-dicyano-2

3-diphenyl-succinate (DCDPS) is a hexa-substituted ethane thermal iniferter and the nickel based catalyst reacted from Ni2+ to Ni1+．The polymerization of styrene (St) was successfully controlled in bulk at 120℃．The kinetics studies showed that the kinetics is first order in monomer．The number average molecular weight Mn increased linearly with conversion from 57100 to 126000

and the molecular weight distributions(Mw／Mn) were around l.5 as the monomer conversion was increased from 38％ to 86％．Well defined polystyrene with α-(carbethoxycyanophenyl)methyl-ω-chlorine end groups was obtained from the polymerization of St with DCDPS／NiCl2／PPh3 initiating system

and the polymerization proceeded via reverse ATRP．While the polymerization behavior of methyl methacrylate (MMA) initiated with the same system was absolutely different．The molecular weights of so-obtained PMMA did not increase with the monomer conversions and at the same time the molecular weight distributions kept narrow (Mw／Mn=1.19) during the polymerization．