Reverse Atom‐Transfer Radical Polymerization at Room Temperature

This paper aims at reporting on the “living”/controlled radical polymerization of methyl methacrylate initiated with the benzoyl peroxide (BPO)/Cu^IX (X=Br,Cl)/2,2'‐bipyridine (bpy) redox system at room temperature. No control is observed for the polymerization conducted in bulk and in toluene, whereas a polymer with predetermined molecular weight and rather narrow molecular weight distribution is formed in butanone. The solvent has thus a decisive effect on the reverse atom‐transfer radical polymerization of methyl methacrylate initiated with the BPO/Cu^IX (X = Br,Cl)/bpy ternary system at 25°C.