Iron-mediated AGET ATRP of Methyl Methacrylate in the Presence of Catalytic Amounts of Base

A novel method for iron‐mediated atom transfer radical polymerization with activators generated by electron transfer (AGET) ATRP of a polar monomer, methyl methacrylate (MMA), is developed in the presence of catalytic amounts of inorganic base NaHCO3 or Na2CO3. The polymerization is carried out using FeCl3 · 6H2O as the catalyst, triphenylphosphine as the ligand, ethyl 2‐bromoisobutyrate as the initiator, and vitamin C as the reducing agent at 70 °C. It is found that the addition of base into the polymerization system enhances the polymerization rate significantly but does not destroy the controllability over the molecular weight and molar‐mass dispersity. Iron‐mediated AGET ATRP of methyl methacrylate is successfully carried out using catalytic amounts of the usual bases, NaHCO3 or Na2CO3, as the additives. The polymerization rate is enhanced significantly in the presence of tiny amounts of base and the polymerization shows features of a “living” radical polymerization.