Corbin Daniel A, McCarthy Blaine G, Miyake Garret M
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA.
Polym Chem. 2020 Aug 21;11(31):4978-4985. doi: 10.1039/d0py00643b. Epub 2020 Jun 30.
An electrochemical variant of organocatalyzed atom transfer radical polymerization (O-ATRP) is developed and investigated. Inspired by electrochemically mediated atom transfer radical polymerization (eATRP), potentiostatic electrolysis is used to manipulate the catalyst's redox states in O-ATRP to understand whether deactivation in O-ATRP can be enhanced to improve polymerization control. During the course of this work, several possible side reactions are investigated, and the electrochemical apparatus is optimized to reduce side reactions at the counter electrode. This electrochemically modified O-ATRP method (eO-ATRP) is then studied at different applied potentials, under different irradiation conditions, and with two photoredox catalysts to understand the impact of electrolysis on polymerization control. Ultimately, although electrolysis was successfully used to improve polymerization control in O-ATRP, some additional challenges have been identified. Several key questions are postulated to guide future work in this area.
开发并研究了有机催化原子转移自由基聚合（O-ATRP）的一种电化学变体。受电化学介导的原子转移自由基聚合（eATRP）的启发，采用恒电位电解来控制O-ATRP中催化剂的氧化还原状态，以了解O-ATRP中的失活是否可以增强以改善聚合控制。在这项工作过程中，研究了几种可能的副反应，并对电化学装置进行了优化，以减少对电极处的副反应。然后在不同的施加电位、不同的辐照条件下，使用两种光氧化还原催化剂研究这种电化学改性的O-ATRP方法（eO-ATRP），以了解电解对聚合控制的影响。最终，虽然电解成功用于改善O-ATRP中的聚合控制，但也发现了一些其他挑战。提出了几个关键问题以指导该领域未来的工作。
