三氟化硼乙醚溶液中卤代芴的电化学聚合  

ELECTROCHEMICAL POLYMERIZATION OF FLUORENE HALIDE IN BORON TRIFLUORIDE DIETHYL ETHERATE SOLUTION

作　　者：陈文[1] 范长利[1] 曾理强[2] 王幸聪[2] 褚奇[1] 徐景坤[2] 

机构地区：[1]成都理工大学材料与化学化工学院,成都610059 [2]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

出　　处：《高分子学报》2008年第9期861-866,共6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(2007GZH1091)资助项目

摘　　要：在三氟化硼乙醚(BFEE)溶液中9-溴芴和9,9-二氯芴可以直接阳极氧化制备聚(9-溴芴)和聚(9,9-二氯芴).单体在BFEE中的起始氧化电位远低于在乙腈体系中的起始氧化电位.聚(9-溴芴)和聚(9,9-二氯芴)均可溶于强极性有机溶剂,如二甲基亚砜、四氢呋喃等,并分别表现出良好的蓝色和黄绿色发光性能,其电导率测定为10-1S/cm.红外光谱和核磁共振波谱表明聚合反应主要发生在2,7位.Poly（9-bromofluorene）（PBF） films and poly（9,9-dichlorofluorene）（PDCF） films were electro-synthesized successfully by direct anodic oxidation of 9-bromofluorene（BF） and 9,9-dichlorofluorene（DCF） using a middle-strong Lewis acid boron trifluoride diethyl etherate（BFEE） as the solvent and the supporting electrolyte containing 0.02 mol/L BF and 0.05 mol/L DCF,respectively.The oxidation potential onset of BF and DCF in pure BFEE was 1.45 V versus SCE and 1.67 V versus SCE,respectively,which were much lower than those determined in acetonitrile containing 0.1 mol L^-1 Bu4NBF4（BF,1.95 V versus SCE and DCF,2.19 V versus SCE）.For spectral analysis,polymers were dedoped with 25% ammonia for 3 days.Then,they were dried at 60℃ for 24 h.For characterization of the structure and properties of as-formed polymers,UV-Vis,fluorescence,FT-IR,and 1H-NMR spectra of the polymers were determined.In the FT-IR spectra of BF or PBF,the peak at 650 cm^-1 was the characteristic absorption of the C—Br bond.Three peaks at 819,759,737 cm^-1 suggested that PBF was 1,2,4-trisubstituted.Similarly,the peak at 802 cm^-1 was the characteristic absorption of the C—Cl bond in the IR spectra of DCF and PDCF.Additionally,the peaks at 867,731,829 cm^-1 indicated that PDCF was also 1,2,4-trisubstituted.FT-IR and 1H-NMR spectral investigations indicated that electrochemical polymerization of BF and DCF mainly occurred at 2,7 positions.According to the UV-Vis spectra of the monomers,the UV-Vis spectra of PBF showed red-shfited absorption at 334 nm,and the PDCF showed broader absorption at 290 nm,342 nm,indicating higher conjugation length of backbone of the polymer.In the fluorescence spectra,the emission peaks of BF and DCF monomers appeared at 334 nm and 338 nm,respectively while those of PBF and PDCF in DMSO appeared at 396 nm and 537 nm,implying the blue-light-emitting property of PBF and the green-light-emitting property of PDCF.The main reason contributing to different light-emitting properties of PBF and PDCF was

关 键 词：聚芴 卤代芴 导电高分子 电化学聚合 三氟化硼乙醚 

分 类 号：O633.5[理学—高分子化学] TQ231.14[理学—化学]