Synthesis of aromatic amine end-functional poly(methyl methacrylate) by atom-transfer radical polymerisation

New poly(methyl methacrylate) bearing aromatic amine end groups has been prepared by atom-transfer radical polymerisation (ATRP) of methyl methacrylate (MMA) using functionalized initiators. Two different methods have been employed. In the first case, nitrophenyl functional initiators were used to obtain nitrophenyl end-functional polymers. Subsequent reduction of the nitro groups yielded the aminophenyl functionality. In the second method, aminophenyl macromonomers were directly prepared using aminophenyl functional initiators. The functionalization of the polymers was quantitative and the molecular weight was well controlled by adjusting the monomer to nitroinitiator molar ratio using NiBr2(PPh3)2 or the CuBr/3BiPyr as a catalyst at 85 °C. These new polymers have application as macromonomers in the synthesis of polyamide and polyimide graft copolymers.