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In order to assess the role of the solvent mediating the disproportionation of Cu(I)X into Cu(0) and Cu(II)X₂ during SET-LRP, a series of polymerizations of methyl acrylate initiated with methyl 2-bromopropionate and catalyzed by Cu(0)/Me₆-TREN at 25 °C in DMSO, MeCN, and their mixtures were investigated. These polymerizations proceed in a dissimilar manner. SET-LRP of MA in DMSO, a solvent that mediates disproportionation, was exemplary of “ultrafast living radical polymerization” with complete conversion in 45 min following the expected first-order kinetics and providing perfect fidelity of the structure of the polymer chain ends. When the polymerization was performed in MeCN, a solvent in which Cu(I)X species do not disproportionate, it displayed nonlinear first-order kinetics with a poor retention of the bromine chain end functionality. The lack of first-order kinetics and decrease of chain end functionality …