Highly Active Ppm Level Organic Copper Catalyzed Photo-induced ICAR ATRP of Methyl Methacrylate

A novel photo-induced homogeneous atom transfer radical polymerization (ATRP) system is constructed using an organic copper salt (Cu(SC(S)N(C2 H5 )2 )2 ) as a photo-induced catalyst at 30 °C. Herein, N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) is used as a ligand, ethyl 2-bromophenylacetate (EBPA) as an ATRP initiator, and (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) as a photo-induced radical initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP using methyl methacrylate (MMA) as a modal monomer. The effect of the concentration of the organic copper on the polymerization is investigated in detail. It is found that well-controlled polymerization can be obtained even with the amount of (Cu(SC(S)N(C2 H5 )2 )2 decreasing to a 1.56 ppm level, with the molecular weight of the resultant polymers increasing linearly with monomer conversion while maintaining a narrow molecular weight distribution (M¯w/M¯n < 1.3).