9,10-二氢化菲在三氟化硼乙醚-浓硫酸混酸中的电化学聚合

在三氟化硼乙醚(BFEE)-浓硫酸混合电解质体系中直接氧化9,10-二氢化菲获得了高质量聚(9,10-二氢化菲)膜, 其电导率为3.8×10－1 S/cm. 9,10-二氢化菲在BFEE＋10%浓硫酸体系中的起始氧化电位为0.93 V vs. SCE, 远低于其在乙腈＋0.1 mol/L Bu4NBF4溶液中的起始氧化电位(1.75 V vs. SCE). 在BFEE＋10%浓硫酸体系中获得的聚(9,10-二氢化菲)膜具有良好的电化学性质. 聚合物部分溶于二甲基亚砜、四氢呋喃、氯仿等极性溶剂. FT-IR和量化计算表明聚合反应主要发生在2, 7位或者3, 6位. 荧光光谱和热重分析表明聚合物是一种良好的蓝色荧光材料且具有良好的热稳定性.

Electrochemical Polymerization of 9,10-Dihydrophenanthrene in Boron Trifluoride Diethyl Etherate Containing Concentrated Sulfuric Acid

High quality poly(9,10-dihydrophenanthrene) (PDHP) films with an electrical conductivity of 3.8×10－1 S/cm were synthesized electrochemically by direct anodic oxidation of 9,10-dihydrophenanthrene in boron trifluoride diethyl etherate (BFEE) containing 10% concentrated sulfuric acid (SA) on a stainless steel electrode. The initial oxidation onset of 9,10-dihydrophenanthrene in BFEE containing 10% SA was only 0.93 V (vs. SCE), which was very much lower than that determined in acetonitrile solution containing 0.1 mol/L Bu4NBF4 (1.75 V vs. SCE). The polymer obtained from this medium showed good electrochemical behavior and could be partly dissolved in dimethylsulfoxide, tetrahydrofuran, chloroform, etc. FT-IR spectra and quantum calculation indicated that the polymerization of monomer occurred mainly at 2,7 or 3,6 positions. Fluorescent spectral studies indicated that the polymer was a blue-light emitter. TG and DTG analyses showed that the as-formed PDHP films had good thermal stability.