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Polymerizations of methyl methacrylate (MMA) monomer initiated by a novel Ni(II)a-benzoinoxime complex have been achieved under homogeneous conditions in the 25-608C temperature range. The activity for polymerization increases with reaction temperature and by carrying out the polymerization in solution of low-polarity solvents without any induction time. The obtained polymers have weight-average molecular weights about 10 5 and slight broad polydispersity indexes (2.2 M w /M n 3.3). Dependence of rate constants polymerization and decomposition of initiator (k app and k d , respectively) on temperature was investigated and activation parameters were computed from Arrhenius plot. 1 H-NMR analysis of PMMA revealed a syndio-rich atactic microstructure in agreement with conventional radical process. Radical scavenger TEMPO effect together with microstructure and molecular weight distributions data supported that the polymerization proceed via free radical mechanism.

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