Photoinduced ICAR ATRP of Methyl Methacrylate with AIBN as Photoinitiator

Abstract

The initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) of methyl methacrylate (MMA) was successfully carried out in N,N-dimethyl formamide (DMF) at ambient temperature under irradiation with N,N,N′,N′-tetramethyl–1,2-ethanediamine (TMEDA) as ligand, azobisisobutyronitrile (AIBN) as photoinitiator, and CCl4 as initiator. The polymerization obeyed the first-order kinetics. Linear increase of the molecular weight distribution (MWD) with monomer conversion and narrow molecular weight distribution were observed. The polymerization proceeded in a living fashion at 15 °C. The apparent activation energy (Eapp) of 27.23 kJ/mol was obtained based on the slope of the plot of ln (kapp) versus (1/T) and the enthalpy (∆Heq 0) was 5.08 kJ/mol. The polymerization was controlled by periodic light on-off. The living character of polymerization was further demonstrated by chain extension with the resulting PMMA-Cl as macrointiator.