Copper(0)‐Mediated Living Radical Polymerization of Methyl Methacrylate in a Non‐polar Solvent

The metal catalyzed polymerization of methyl methacrylate using Cu(0) as the catalyst source has been investigated in toluene. This work looks at polymerizations in a non‐polar medium allowing control over the molecular weight and polydispersity with a 4‐fold reduction in catalyst concentration versus conventional ATRP, while the use of an active ligand allows the reaction to proceed at room temperature. The use of an excess of PMDETA ligand allows for high conversions, and the addition of a small amount of CuBr₂ enhances living characteristics, enabling efficient chain extension.