title: Facile "living" radical polymerization of methyl methacrylate in the presence of iniferter agents: homogeneous and highly efficient catalysis from copper(II) acetate.
abstract: 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.
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
authors.forename: Hongjuan
authors.initials: H
authors.lastname: Jiang
authors.forename: Lifen
authors.initials: L
authors.lastname: Zhang
authors.forename: Xiaowu
authors.initials: X
authors.lastname: Jiang
authors.forename: Xiaoguang
authors.initials: X
authors.lastname: Bao
authors.forename: Zhenping
authors.initials: Z
authors.lastname: Cheng
authors.forename: Xiulin
authors.initials: X
authors.lastname: Zhu
mesh_terms: D002384:Catalysis; D005609:Free Radicals / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D020366:Methylmethacrylate / Q000737:chemistry*; D008970:Molecular Weight; D009942:Organometallic Compounds / Q000737:chemistry*; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D009942:Organometallic Compounds; D011108:Polymers; D020366:Methylmethacrylate; C015092:cupric acetate
keywords: copper(II) acetate; dithiocarbamate; “living” radical polymerization