ATRP of Methacrylates Utilizing CuIIX2/L and Copper Wire

Methacrylate monomers were successfully polymerized by ATRP utilizing copper wire as an in situ reducing agent at near-ambient temperatures (35 °C). Well-controlled polymerizations were demonstrated with both PMDETA and dNbpy ligands. Polymerization rates, when conducted with PMDETA, were dependent on the surface area of Cu0. Upon reduction of the copper deactivator concentration (i.e., CuIIBr2), polymerizations would only occur in the presence of excess ligand, whereas polymerization rates were independent of [CuIIBr2]. Proper selection of initiator and copper halide improved polymerization control with PMDETA. dNbpy was found to be an excellent ligand for MMA, resulting in polymerization systems with controlled behavior, predetermined molecular weights, narrow molecular weight distributions (Mw/Mn ≤ 1.2), and near-quantitative initiation. The versatility of dNbpy was demonstrated by polymerization of a wide range of methacrylates, synthesis of polymethacrylates with molecular weights up to 80 000, and efficient chain extension of a PMMA macroinitiator.