Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213 (USA).
Angew Chem Int Ed Engl. 2015 Feb 16;54(8):2388-92. doi: 10.1002/anie.201410598. Epub 2015 Jan 7.
Simplification of electrochemically mediated atom transfer radical polymerization was achieved efficiently under either potentiostatic or galvanostatic conditions using an aluminum wire sacrificial anode (seATRP) immersed directly into the reaction flask without separating the counter electrode. seATRP polymerizations were carried out under different applied potentials, Eapps = E1/2, Epc, Epc -40 mV, and Epc -80 mV. As the rate of polymerization (Rp) can be modulated by applying different Eapp potentials, more reducing conditions resulted in faster Rp. The polymerization results showed similar narrow molecular-weight distribution throughout the reactions, similar to results observed for n-butyl acrylate (BA) polymerization under conventional eATRP. High-molecular-weight PBA and diblock copolymers were synthesized by seATRP with more than 90% monomer conversion. Furthermore, galvanostatic conditions were developed for synthesizing PBA with the two-electrode system.
通过使用直接浸入反应瓶中的铝丝牺牲阳极（seATRP），在恒电位或恒电流条件下，有效地简化了电化学介导的原子转移自由基聚合，无需分离对电极。在不同的施加电位下进行了 seATRP 聚合，Eapps = E1/2、Epc、Epc -40 mV 和 Epc -80 mV。由于聚合速率（Rp）可以通过施加不同的 Eapp 电位来调节，因此还原条件越强，Rp 越快。聚合结果表明，整个反应过程中的分子量分布相似，与传统的 eATRP 下的 n- 丁基丙烯酰胺（BA）聚合结果相似。通过 seATRP 合成了具有高分子量的 PBA 和嵌段共聚物，转化率超过 90%。此外，还开发了通过两电极系统合成 PBA 的恒电流条件。
