https://scholars.lib.ntu.edu.tw/handle/123456789/624026
標題: | Copper-mediated CRP of methyl acrylate in the presence of metallic copper: Effect of ligand structure on reaction kinetics | 作者: | Zhang Y. Wang Y. CHI-HOW PENG Zhong M. Zhu W. Konkolewicz D. Matyjaszewski, K. |
公開日期: | 2012 | 卷: | 45 | 期: | 1 | 起(迄)頁: | 78-86 | 來源出版物: | Macromolecules | 摘要: | The kinetics of copper-mediated controlled/living radical polymerization (CRP) of methyl acrylate (MA) in the presence of Cu 0 and two different ligands that form active catalyst complexes with copper-TPMA (tris(2-pyridylmethyl)amine) and Me 6TREN (tris(2-(dimethylamino) ethyl)amine)-are compared. The critical difference between the ligands is that TPMA forms a Cu I complex that undergoes essentially no disproportionation in a mixture of MA and dimethyl sulfoxide (DMSO), DMSO/MA (v/v = 1/2), while the complex with Me 6TREN undergoes disproportionation to a limited extent. Parameters such as the surface area of Cu 0 wire, the concentration of added Cu IIX 2/L, and ligand concentration were examined. Both the Me 6TREN- and TPMA-based catalysts efficiently controlled the polymerization of MA. The TPMA-based system showed a power law order of 0.47 for the apparent propagation rate constant with the Cu 0 surface area, very similar to the reported value for the Me 6TREN-based system, which showed a power law of 0.44. These results demonstrate that the polymerization of MA in DMSO in the presence of metallic copper can be explained by a core atom-transfer radical polymerization (ATRP) process in which the Cu 0 acts as a supplemental activator and reducing agent, rather than through the proposed single-electron-transfer living radical polymerization (SET-LRP) mechanism, which requires additional assumptions, such as complete and instantaneous disproportionation of Cu I/L species. ? 2011 American Chemical Society. |
URI: | https://www.scopus.com/inward/record.uri?eid=2-s2.0-84862909355&doi=10.1021%2fma201963c&partnerID=40&md5=b0e0d75a6d1c64797f87e9ea7dbc8f65 https://scholars.lib.ntu.edu.tw/handle/123456789/624026 |
DOI: | 10.1021/ma201963c | SDG/關鍵字: | Active catalyst;Controlled/living radical polymerization;Disproportionations;Ligand concentration;Ligand structure;Living radical polymerization;Metallic copper;Methyl acrylates;Power law;Propagation rate constant;SET-LRP;Surface area;Acrylic monomers;Catalysts;Copper;Copper compounds;Copper metallurgy;Dimethyl sulfoxide;Free radical reactions;Ligands;Living polymerization;Organic compounds;Organic solvents;Polymers;Rate constants;Reaction kinetics;Transients;Atom transfer radical polymerization |
顯示於: | 化學系 |
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