Kinetic insight into electrochemically mediated ATRP gained through modeling

被引：43
作者：
Guo, Jun-Kang [1 ]
Zhou, Yin-Ning [1 ]
Luo, Zheng-Hong [1 ]
机构：
[1] Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Dept Chem Engn, Shanghai 200240, Peoples R China
来源：
AICHE JOURNAL | 2015年 / 61卷 / 12期
基金：
中国国家自然科学基金; 国家高技术研究发展计划(863计划);
关键词：
electrochemically mediated ATRP; kinetic model; polymerization mechanism; overpotential; TRANSFER RADICAL POLYMERIZATION; DIFFUSION-CONTROLLED REACTIONS; BUTYL ACRYLATE; ARGET ATRP; ICAR ATRP; CATALYST CONCENTRATION; ELECTRON-TRANSFER; RATE COEFFICIENTS; METALLIC COPPER; CU CATALYST;
D O I：
10.1002/aic.14969
中图分类号：
TQ [化学工业];
学科分类号：
0817 ;
摘要：
A detailed kinetic model was constructed using the method of moments to elucidate the electrochemically mediated atom transfer radical polymerization (eATRP). Combined with electrochemical theory, the reducing rate coefficient relevant to the overpotential in eATRP was coupled into the kinetic model. The rate coefficients for eATRP equilibrium and the reducing rate coefficient were fitted to match the experimental data. The effects of catalyst loading, overpotential, and application of programmable electrolysis on the eATRP behavior were investigated based on the tested kinetic model. Results showed that the apparent polymerization rate exhibited a square root dependence on catalyst loading. In addition, a more negative potential accelerated the polymerization rate before the mass transport limitation was reached. This phenomenon indicated that the polymerization rate could be artificially controlled by the designed program (i.e., stepwise and intermittent electrolysis programs). What is more, the normal ATRP, photo-ATRP, and eATRP were compared to obtain a deeper understanding of these ATRP systems. (c) 2015 American Institute of Chemical Engineers
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收藏
页码：4347 / 4357
页数：11
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