Ambient temperature rapid ATRP of methyl acrylate, methyl methacrylate and styrene in polar solvents with mixed transition metal catalyst system

Ambient temperature atom transfer radical polymerization (ATRP) of methyl acrylate (MA), methyl methacrylate (MMA) and styrene (Sty) in the presence of polar solvents (dimethyl sulfoxide: DMSO, dimethylformamide: DMF and acetonitrile: MeCN) with a mixed transition metal catalyst system (Fe(0) as initial activator and CuBr2/Me6TREN complex as deactivator) provides a rapid synthesis of polymers with very low polydispersity (PDI) values and predetermined molecular weights. The polymethylacrylate (PMA) prepared using this novel approach contains the Br-terminated chain ends (functionality ∼100%) and can be successfully used for block copolymer synthesis (as demonstrated on the chain extension experiment performed using the PMA–Br macroinitiator). The key elementary reactions involved in this novel ATRP system and some preliminary mechanistic aspects of the process are also discussed.