Reverse Atom Transfer Radical Polymerization Using AIBN or BPO as Initiator

The reverse atom transfer radical polymerization (ATRP) of methyl acrylate can be realized with the initiating system, AIBN/CuCl2/bpy, in bulk by means of a new polymerization procedure. The reverse ATRP of styrene is also accessible using BPO/CuCl2/bpy as the initiating system. The initiation mechanism in reverse ATRP with BPO is different from that with AIBN due to the redox reaction between BPO and CuI generated from the reaction of radicals with CuII. The "living"/Vcontrolled radical polymerization of methyl methacrylate and styrene can be implemented using BPO/CuICl/bpy as the initiating system in solvents at ambient temperature (40°C). The mechanism suggested the initiation is a redox reaction, and the propagation is identical with that of ATRP.