Department of Electronic Chemistry, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan) http://www.echem.titech.ac.jp/∼inagi/e-index.html.
Angew Chem Int Ed Engl. 2015 Mar 23;54(13):3922-6. doi: 10.1002/anie.201412391. Epub 2015 Feb 20.
We report the first ever use of electrochemically mediated atom transfer radical polymerization (eATRP) employing a bipolar electrochemical method for the fabrication of both gradient and patterned polymer brushes. A potential gradient generated on a bipolar electrode allowed the formation of a concentration gradient of a Cu(I) polymerization catalyst through the one-electron reduction of Cu(II) , resulting in the gradient growth of poly(NIPAM) brushes from an initiator-modified substrate surface set close to a bipolar electrode. These polymer brushes could be fabricated in three-dimensional gradient shapes with control over thickness, steepness, and modified area by varying the electrolytic conditions. Moreover, by site-selective application of potential during bipolar electrolysis, a polymer brush with a circular pattern was successfully formed. Polymerization was achieved using both a polar monomer (NIPAM) and a nonpolar monomer (MMA) with the eATRP system.
我们首次报告了使用双极电化学方法进行电化学介导的原子转移自由基聚合（eATRP），用于制备梯度和图案化聚合物刷。双极电极上产生的电势梯度允许通过单电子还原 Cu(II)形成 Cu(I)聚合催化剂的浓度梯度，从而导致聚（NIPAM）刷从靠近双极电极的引发剂修饰的基板表面开始进行梯度生长。通过改变电解条件，可以控制厚度、陡度和改性区域来制备具有三维梯度形状的聚合物刷。此外，通过在双极电解过程中选择性地施加电位，可以成功形成具有圆形图案的聚合物刷。该 eATRP 体系可以实现极性单体（NIPAM）和非极性单体（MMA）的聚合。
