Living radical polymerization of methyl methacrylate with a zerovalent nickel complex, Ni(PPh3)41

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A zerovalent nickel complex, Ni(PPh 3 ) 4 , induced living radical polymerization of methyl methacrylate (MMA) in conjunction with an organic bromide as an initiator [R-Br: CCl 3 Br, (CH 3 ) 2 C(CO 2 Et)Br, (CH 3 ) 2 C(COPh)Br] in the presence of Al(Oi-Pr) 3 additive. The molecular weight distributions were narrow (M w /M n ∼ 1.2) throughout the reactions, and the number-average molecular weights (M n ) increased in direct proportion to monomer conversion. In contrast, the polymers obtained with CCl 4 in place of R-Br had broader MWDs (M w /M n > 2). The Al(Oi-Pr) 3 additive should be added for the smooth polymerizations of MMA to occur, similarly to those with a divalent nickel bromide, NiBr 2 (PPh 3 ) 2 . The Ni(PPh 3 ) 4 -mediated living polymerization apparently proceeds via the activation of the C-Br bond from the initiators R-Br, assisted by the redox reaction of the complex between Ni(0) and Ni(I) species.

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