A recent publication in Macromol. Rapid Commun. by Prof. Bao Xiaoguang and Prof. Cheng Zhenping
Facile "Living" Radical Polymerization of Methyl Methacrylate in the Presence of Iniferter Agents: Homogeneous and Highly Efficient Catalysis from Copper(II) Acetate


Hongjuan Jiang
,   Lifen Zhang,   Xiaowu Jiang,   Xiaoguang Bao*  (鲍晓光),   Zhenping Cheng*  (程振平)  and   Xiulin Zhu*  (朱秀林)


Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China

Macromol. Rapid Commun. 2014, 35, 1332-1339

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. 1H NMR spectra and chain-extension experiments further confirm the "living" characteristics of this process. A plausible mechanism is discussed.


Link: 
http://onlinelibrary.wiley.com/doi/10.1002/marc.201400204/full