Kinetic Insights into the Iron-Based Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate
Kinetic Insights into the Iron-Based Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate
复制标题
甲基丙烯酸甲酯铁基电化学介导的原子转移自由基聚合的动力学见解
DOI：
10.1021/acs.macromol.6b01022
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发表时间：
2016-06-14
期刊：
影响因子：
5.5
通讯作者：
Luo, Zheng-Hong
中科院分区：
文献类型：
--
作者：
Guo, Jun-Kang;Zhou, Yin-Ning;Luo, Zheng-Hong
首次建立了一种基于甲基丙烯酸甲酯（MMA）和铁的电化学介导原子转移自由基聚合（erap）体系。系统地研究了其动力学行为，包括外加电位和催化剂负载的影响。结果表明，负极电位越大，聚合速度越快，直至达到传质极限。然而，减少催化剂负载会对聚合行为产生不利影响，如聚合速率降低和分子量分布（M/Mn）增加。此外，还建立了基于矩量法的动力学模型来解释Mn和Mn的失配，仿真结果表明，慢起爆对该体系的动力学行为有显著影响。采用溴化铁（II）催化的正态ATRP、溴化铁（III）催化的ATRP和溴化铜（II）催化的ATRP，比较并定性地阐明了它们各自的聚合反应动力学特征。本研究从聚合动力学的角度将eratp的范围从铜基体系扩展到铁基体系，希望能促进该方法的广泛应用。
An iron- and methyl methacrylate (MMA)-based electrochemically mediated atom transfer radical polymerization (eATRP) system was developed for the first time. Kinetic behaviors, including the effect of applied potential and catalyst loading, were systematically investigated. Results indicated that with more negative electrode potential, the polymerization rate increased until the mass transport limitation was reached. However, reduction of the catalyst loading had adverse effects on polymerization behaviors, such as decreased polymerization rate and increased molecular weight distributions (M/Mn). In addition, a kinetic model based on the method of moments was also constructed to explain the mismatch in Mn and Mn,theo" Simulation results showed that slow initiation significantly influenced on the kinetic behaviors in this system. Iron(II) bromide -catalyzed normal ATRP, iron(III) bromide catalyzed eATRP, and copper(II) bromide -catalyzed eATRP were conducted to compare and elucidate their respective polymerization reaction kinetic characteristics qualitatively. This work expanded the scope of eATRP from a copper -based system to an iron -based system in terms of polymerization kinetics, with the hope of promoting the widespread application of this method.