四氢呋喃/三氟化硼乙醚混合电解质中咔唑的电化学聚合  

ELECTROPOLYMERIZATION OF CARBAZOLE IN MIXED ELECTROLYTE OF TETRAHYDROFURAN AND BORON TRIFLUORIDE DIETHYL ETHERATE

作　　者：申艳艳[1] 苗华明[1,2] 徐景坤[1] 张洪林[2] 卢宝阳[1] 

机构地区：[1]江西科技师范学院江西省有机功能分子重点实验室,南昌330013 [2]曲阜师范大学化学科学学院,曲阜273165

出　　处：《高分子学报》2008年第11期1089-1095,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号50663001);教育部重点科技项目(项目号2007-207058);江西省自然科学基金(基金号2007GZH1091);江西省教育厅基金(基金号GJJ08369)资助项目

摘　　要：在四氢呋喃/三氟化硼乙醚混合电解质中直接阳极氧化咔唑制备聚咔唑.单体的起始氧化电位为0.92 Vversus SCE,远低于单体在含0.1 mol.L-1Bu4NBF4的乙腈溶液中的起始氧化电位(1.36 Vversus SCE).在此体系中获得的聚咔唑膜具有良好的电化学活性和稳定性,其电导率为7.0×10-3S.cm-1.聚合物可部分溶解于二甲基亚砜等强极性有机溶剂.UV-Vis,FT-IR,1H-NMR证明聚合物共轭长链的形成.该体系中获得的聚咔唑是一种蓝光发射材料,并具有良好的热稳定性.The purpose of this work is to decrease the amount of boron trifluoride diethyl etherate （BFEE） usually used during the electrochemical polymerization and enhance the stability of as-formed polymer films. The mixed electrolyte of tetrahydrofuran （THF） and BFEE was used because THF can form a new complex with BF3 which is more stable than BFEE and it also can be the solvent for many kinds of aromatic compound which can be electropolymerized. To increase the ionic conductivity of the mixed electrolyte, Bu4 NBF4 was introduced. The ionic conductivity of THF containing 18 % BFEE （by volume） and 0.1 mol· L^-1 Bu4 NBF4 was measured to be 1.25 ×10^-3 S· cm^-1. In this medium, high-quality polycarbazole （PCZ） films were electrosynthesized successfully by direct oxidation of 0.05 mol·L^-1 carbazole. The oxidation potential of carbazole in this medium was measured to be only 0.92 V versus SCE, which was much lower than that determined in acetonitrile containing 0.1 mol·L^-1 Bu4 NBF4 （1.36 V versus SCE）. PCZ films obtained from this medium showed good electrochemical behavior, with electrical conductivity of 7.0 × 10^-3 S·cm^-1. As-formed PCZ films can be partly dissolved in strong polar organic solvents such as dimethyl sulfoxide. For dedoping, PCZ films were treated with 25 % ammonia for 3 days. Then, they were dried at 60℃ for 24 h. The UV-Vis spectra of PCZ showed broader absorption bands mainly at 303 nm, implying wide molar mass distribution. In the fluorescence spectra, the emission peaks of polycarbazole appeared at 415 nm, implying the blue-light-emitting property of PCZ. The FT-IR and ^1H-NMR spectral investigations of PCZ indicated that electrochemical polymerization of carbazole mainly occurred at 3,6 positions, in well accordance with the literature reported previously. Thermal analyses indicated that PCZ films prepared from this medium own good thermal stability. The successful electrosyntheses of PCZ films in this mixed electrolyte may extend the applications of this mixed electro

关 键 词：聚咔唑 导电高分子 电化学聚合 混合电解质 四氢呋喃 三氟化硼乙醚 

分 类 号：O633.5[理学—高分子化学]