Synthesis and characterization of polythiophene grafted with a nitroxide radical polymer via atom transfer radical polymerization
Synthesis and characterization of polythiophene grafted with a nitroxide radical polymer via atom transfer radical polymerization
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DOI：
10.1039/c2py20048a
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发表时间：
2012-05
影响因子：
4.6
通讯作者：
Chun-Hao Lin;Chi-Min Chau;J. Lee
中科院分区：
文献类型：
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作者：
Chun-Hao Lin;Chi-Min Chau;J. Lee
报道了2，5-poly(3-[1-ethyl-2-(2-bromoisobutyrate)]thiophene)-graft-poly(2，2，6，6-tetramethylpiperidin-1-oxyl-4-yl-g-PTMA的合成及其在有机基电池中的电化学性能。以3-[1-乙基-2-(2-溴异丁酸酯)]噻吩接枝聚(2，2，6，6-四甲基哌啶-4-甲基丙烯酸酯)(PTMPM)为引发剂，通过原子转移自由基聚合(ATRP)合成了聚噻吩型大分子引发剂PEBBT-g-PTMPM。通过对一系列模型聚合反应的考察，优化了2，2，6，6-四甲基哌啶-4-甲基丙烯酸酯(TMPM)的ATRP反应条件。用间氯过氧苯甲酸氧化PEBBT-g-PTMPM，得到相对分子质量较高的PEBBT-g-PTMA(mN=483 300)，防止聚合物溶解到电解液中。PEBBT-g-PTMA已被评价为可充电有机基电池的正极活性材料。循环伏安测试结果表明，在约3.6V(vs.Li/Li+)处有一个氧化还原对。电池性能测试表明，有机基电池具有良好的电化学稳定性和循环性能。
Synthesis of 2,5-poly(3-[1-ethyl-2-(2-bromoisobutyrate)]thiophene)-graft-poly(2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl methacrylate) (PEBBT-g-PTMA) and its electrochemical properties in organic radical batteries have been reported. The polythiophene-based macroinitiator PEBBT, synthesized from 3-[1-ethyl-2-(2-bromoisobutyrate)]thiophene, grafts with poly(2,2,6,6-tetramethylpiperidin-4-yl methacrylate) (PTMPM) to yield PEBBT-g-PTMPM via atom transfer radical polymerization (ATRP). The conditions for ATRP of 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPM) are optimized by examining a series of model polymerizations. PEBBT-g-PTMPM is oxidized by m-chloroperoxybenzoic acid to yield PEBBT-g-PTMA with a relatively high molecular weight (Mn = 483 300) that prevents the dissolution of the polymer into electrolytes. PEBBT-g-PTMA has been evaluated as a cathode-active material in a rechargeable organic radical battery. The result of cyclic voltammetry shows a redox couple at approximately 3.6 V (vs. Li/Li+). Furthermore, the cell performance shows that the organic radical battery has good electrochemical stability and good cyclability.