Iron‐mediated AGET ATRP of methyl methacrylate using metal wire as reducing agent

Methyl methacrylate (MMA) were successfully polymerized by atom transfer radical polymerization with activator generated by electron transfer (AGET ATRP) using copper or iron wire as the reducing agent at 90°C. Well‐controlled polymerizations were demonstrated using an oxidatively stable iron(III) chloride hexahydrate (FeCl3·6H2O) as the catalyst, ethyl 2‐bromoisobutyrate (EBiB) as the initiator, and tetrabutylammonium bromide (TBABr) or triphenylphosphine as the ligand. The polymerization rate was fast and affected by the amount of catalyst and type of reducing agents. For example, the polymerization rate of bulk AGET ATRP with a molar ratio of [MMA]0/[EBiB]0/[FeCl3·6H2O]0/[TBABr]0 = 500/1/0.5/1 using iron wire (the conversion reaches up to 82.2% after 80 min) as the reducing agent was faster than that using copper wire (the conversion reaches up to 86.1% after 3 h). At the same time, the experimental Mn values of the obtained poly(methyl methacrylate) were consistent with the corresponding theoretical ones, and the Mw/Mn values were narrow (∼1.3), showing the typical features of “living”/controlled radical polymerization.