Bulk AGET ATRP of methyl methacrylate using iron(iii) acetylacetonate as a catalyst

In this work, polymerization of methyl methacrylate (MMA) was successfully conducted by atom transfer radical polymerization with activators generated by electron transfer (AGET ATRP) at 90 °C, using iron(III) acetylacetonate (Fe(acac)3) as a catalyst, ethyl alpha-bromophenylacetate (EBPA) as an initiator, ascorbic acid (AsAc) as a reducing agent and triphenyl phosphine (PPh3) as a ligand. The polymerization kinetics showed that the polymerization rate (the conversion reached up to 98.1% after 60 min) was much higher than that mediated by inorganic iron salts and it was affected by the feed of the iron catalyst. Moreover, the kinetic plots were linear, and the molecular weights of the resulting polymers with molecular weight distribution around 1.2, increased linearly with monomer conversions, indicating good features of “living”/controlled radical polymerizations. The end-functionality of the polymers was confirmed by 1H NMR spectroscopy and a chain extension experiment.