ATRP of MMA Catalyzed by FeIIBr2 in the Presence of Triflate Anions

FeIIBr2-catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in polar solvents without any additional ligand was reported. FeIIBr2/TBAOTf-catalyzed ATRP of MMA with different targeted degrees of polymerization (DP) was evaluated in 33.3% anisole at 60°C. FeII-(OTf)2 is found to be soluble in anisole but has very low activity in ATRP without any additional halide ligand. The PMMA macroinitiator is synthesized using molar ratio of reagents and is obtained as a white powder with slightly higher molecular weight. A very small amount of dead chains are observed after chain extension, indicating well-preserved chain-end functionality. The catalyst activity and the level of control over the polymerization did not change with increasing ratio of TBAOTf, once FeIIBr2 is completely dissolved.