A copper‐based reverse ATRP process for the living radical polymerization of methyl methacrylate

The reverse atom transfer radical polymerization (RATRP) technique using CuCl 2 /bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of methyl methacrylate (MMA). A hexa‐substituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was used as the initiator in this copper‐based reverse ATRP initiation system. The reversible dissociation nature of DCDPS gives a more suitable amount of primary radical than formerly used conventional initiators, such as AIBN. High molecular weight and narrow molecular weight distribution ( M w /M n ≈ 1.20) of the resulting PMMA was obtained in bulk and in solution polymerization at 85°C. End‐group analysis result by 1 H‐NMR spectroscopy shows that the polymer obtained is ω‐functionalized by a chlorine group, which can be used as macroinitiator for chain extension and block copolymerization with a conventional ATRP catalyst.