Controlled radical polymerization catalyzed by CuCl/BDE complex in water medium. II. Polymerization of methyl methacrylate and formation of PMMA with bimodal molecular weight distribution

The emulsion polymerization of MMA was explored for the BDE/CuCl coordinated catalyst. The Mn of PMMA linearly increased both with increasing the monomer conversion and the proceeding polymerization time, which means that the MMA polymerized in “living”/controlled characters with zero order kinetics...

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Bibliographic Details
Published in:Journal of applied polymer science 2002-04, Vol.83 (14), p.3076-3081
Main Authors: Wan, Xiaolong, Liu, Yanfei, Ying, Shengkang
Format: Article
Language:English
Subjects:
"living"/controlled radical polymerization
Applied sciences
bimodal molecular weight distribution
bis(dimethylaminoethyl) ether
emulsion polymerization
Exact sciences and technology
methyl methacrylate
Organic polymers
Physicochemistry of polymers
Properties and characterization
Solution and gel properties
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Summary:The emulsion polymerization of MMA was explored for the BDE/CuCl coordinated catalyst. The Mn of PMMA linearly increased both with increasing the monomer conversion and the proceeding polymerization time, which means that the MMA polymerized in “living”/controlled characters with zero order kinetics under BDE/CuCl‐catalyzed emulsion conditions. The apparent polymerization rate constants of MMA were k [MMA]=3.0Mapp = 0.765 mol/min, k [MMA]=1.8Mapp = 0.760 mol/min at 80°C, while k [MMA]1.8Mapp = 0.228 mol/min at 50°C, respectively. Slight differences of polymerization results were obtained when emulsifier lauryl phosphate (ADP) and Polyoxyethylene nonyl phenyl ether (OP‐10) were adapted in the polymerization. Based on the “coordinated radical cage” mechanism proposed particularly to the BDE/CuCl catalyzed polymerization, reversible equilibrium between common free radical and the coordinated “living” species should exist in this system. Increasing the amount of catalyst must affect the fast equilibrium between those two species, thus, also affecting the relative content in the emulsion circumstance. Therefore, PMMA, with bimodal molecular weight distribution, was achieved through this approach. The formation of PMMA with bimodal distribution was affected by concentration of catalyst and polymerization temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3076–3081, 2002; DOI 10.1002/app.2336
ISSN:0021-8995
1097-4628
DOI:10.1002/app.2336