Self-activation and activation of Cu(0) wire for SET-LRP mediated by fluorinated alcohols

Herein we report the self-activation and activation of Cu(0) wire used to form a catalyst in single-electron transfer living radical polymerization (SET-LRP) in two fluorinated alcohols employed as solvents, 2,2,2-trifluoroethanol (TFE) and 2,2,3,3-tetrafluoropropanol (TFP). Self-activation and activation of Cu(0) wire by TFP exhibit a stronger increase of the apparent rate constant of propagation, k(p)(app), compared to TFE. SET-LRP of methyl acrylate (MA) in DMSO catalyzed with TFP-activated Cu(0) wire showed a comparable k(p)(app) value to that of the hydrazine-activated Cu(0) wire-catalyzed counterpart. SET-LRP catalyzed with Cu(0) wire pretreated with TFE or TFP, and the in situ activation of Cu(0) wire while using TFE or TFP as solvent, proceeded with no initial induction period and exhibits predictable molecular weight evolution with conversion and narrow molecular weight distribution.