Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate Catalyzed by FeCl3 · 6H2O/MA5‐DETA System

Abstract

A new kind of multidentate aliphatic amine, N,N,N′,N″,N″‐penta(methyl acylate)diethylenetriamine (MA5‐DETA), was explored to be the ligand of Fe compound. Ferric chloride hexahydrate (FeCl3 · 6H2O) coordinated by MA5‐DETA was successfully used as the catalyst in 2,2′‐azobisisobutyronitrile (AIBN) initiated reverse atom transfer radical polymerization (RATRP) of methyl methacrylate (MMA). Under various reaction conditions, including the different initiating system concentrations and ratios of transition metal to ligand and catalyst concentrations, the bulk polymerization showed “living”/controlled nature. The number‐average molecular weight (M n) of the polymer increased linearly with monomer conversion and the polydispersity (M w/M n) was low (1.1 < M w/M n < 1.5). The results of the solution RATRP of MMA in different solvents indicated that the polymerization rate in polar solvents was much faster than that in non‐polar solvents. All the results indicated FeCl3 · 6H2O/MA5‐DETA was a kind of non‐toxic, cheap, readily available catalyst with high activity for the RATRP of MMA.