Facile “Living” Radical Polymerization of Methyl Methacrylate in the Presence of Iniferter Agents: Homogeneous and Highly Efficient Catalysis from Copper(II) Acetate

A facile homogeneous polymerization system involving the iniferter agent 1‐cyano‐1‐methylethyl diethyldithiocarbamate (MANDC) and copper(II) acetate (Cu(OAc) 2 ) is successfully developed in bulk using methyl methacylate (MMA) as a model monomer. The detailed polymerization kinetics with different molar ratios (e.g., [MMA] 0 /[MANDC] 0 /[Cu(OAc) 2 ] 0 = 500/1/x (x = 0.1, 0.2, 0.5, 1.0)) demonstrate that this system has the typical “living”/controlled features of “living” radical polymerization, even with ppm level catalyst Cu(OAc) 2 , first order polymerization kinetics, a linear increase in molecular weight with monomer conversion and narrow molecular weight distributions for the resultant PMMA. 1 H NMR spectra and chain‐extension experiments further confirm the “living” characteristics of this process. A plausible mechanism is discussed.