Facile synthesis of well-defined redox responsive diselenide-labeled polymers via organoselenium-mediated CRP and aminolysis
Feng Gaoa, Xiangqiang Pan*a(潘向强), Jian Zhua, Zhengbiao Zhang*a(张正彪), Wei Zhanga and Xiulin Zhua
a Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Polym. Chem. 2015, 6, 1367-1372
Diselenide-containing polymer is an attractive polymer for their redox sensitivity, and has potential applications in bio-related areas. In this work, the synthesis of diselenide (Se–Se)-labeled polymers based on diselenocarbonate-mediated controlled radical polymerization (CRP) was investigated. Diselenocarbonate-end capped polymers from diselenocarbonate-mediated CRP were transformed to diselenide-centered polymers through high-efficiency aminolysis and a spontaneous oxidation coupling reaction in an open system. The process of aminolysis and spontaneous oxidation of the polymer chain ends was monitored by UV-Vis, GPC and NMR characterizations. The obtained diselenide-centered polymers showed reversible redox-responsive behavior. This work provides a protocol for introducing a redox responsive Se–Se bond into the polymer backbones. Importantly, the molecular weight and architectures of the diselenide-containing polymer can be well defined, which would be potentially useful for the fabrication of bio-related polymeric materials.