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郭君康, 周寅宁, 罗正鸿. 电化学调控原子转移自由基聚合动力学模拟初步研究[J]. 应用技术学报, 2017, 17(1): 14-21, 31. DOI: 10.3969/j.issn.2096-3424.2017.01.004
引用本文: 郭君康, 周寅宁, 罗正鸿. 电化学调控原子转移自由基聚合动力学模拟初步研究[J]. 应用技术学报, 2017, 17(1): 14-21, 31. DOI: 10.3969/j.issn.2096-3424.2017.01.004
GUO Junkang, ZHOU Yinning, LUO Zhenghong. Preliminary Study on Kinetic Modeling of Electrochemically Mediated Atom Transfer Radical Polymerization[J]. Journal of Technology, 2017, 17(1): 14-21, 31. DOI: 10.3969/j.issn.2096-3424.2017.01.004
Citation: GUO Junkang, ZHOU Yinning, LUO Zhenghong. Preliminary Study on Kinetic Modeling of Electrochemically Mediated Atom Transfer Radical Polymerization[J]. Journal of Technology, 2017, 17(1): 14-21, 31. DOI: 10.3969/j.issn.2096-3424.2017.01.004

电化学调控原子转移自由基聚合动力学模拟初步研究

Preliminary Study on Kinetic Modeling of Electrochemically Mediated Atom Transfer Radical Polymerization

  • 摘要: 基于矩方法建立了电化学调控原子转移自由基聚合(eATRP)的动力学模型.利用该模型分析了eATRP与普通ATRP之间的区别, 并模拟了过电位、催化剂浓度和引发剂浓度对聚合反应的影响.模拟结果表明, 过电位的增大对聚合反应速率的促进作用明显, 但聚合物分散指数(PDI)不变; 增大催化剂浓度可以提高聚合反应速率, 同时降低PDI.当催化剂含量(催化剂与单体浓度之比)低至3×10-5时, PDI在反应时间内不能达到稳定且其值高达1.2以上; 引发剂的影响主要体现在反应的诱导期长短上, 当引发剂与单体浓度比下降至0.5:300时, 诱导期从200s迅速增大到400s左右.

     

    Abstract: A detailed kinetic model about electrochemically mediated atom transfer radical polymerization (eATRP) was constructed by the method of moments. Based on the model, the difference between eATRP and normal ATRP was elucidated, and the effects of overpotential, catalyst loading and initiator concentration on polymerization behavior were predicted. The results show that overpotential and catalyst concentration both have a positive effect on the polymerization rate, while the former has no influence on the polydispersity index (PDI) and the later reduces the PDI. When the catalyst concentration (ratio of the catalyst and monomer concentration) decreases to 3× 10-5, PDI is as high as 1.2 and cannot get steady within the reaction time. Besides, the initiator concentration mainly affects the induction period of the reaction. When the ratio of the initiator concentration to the monomer concentration declines to 0.5:300, the induction period is extended from 200 s to about 400 s rapidly.

     

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