【作者】 侯健；

【导师】 张书圣； 徐景坤；

【作者基本信息】 青岛科技大学 ， 应用化学， 2006， 硕士

【摘要】 电化学方法是制备导电聚合物的重要方法。本论文采用三氟化硼乙醚体系成功地制备了高性能聚硒吩、聚荧蒽、聚5位卤素取代吲哚（包括聚5氟吲哚、聚5氯吲哚和聚5溴吲哚）。同时对获得的聚合物进行了表征。三氟化硼乙醚是一种中等强度的Lewis酸，它与芳香化合物单体相互作用，能有效降低单体的氧化电位，从而提高聚合物性能。 1、首次在三氟化硼乙醚体系中成功地制备了电导率为2.8×10^-1S cm^-1的高性能聚硒吩膜，硒吩的氧化电位在三氟化硼乙醚中比在乙腈中低0.6V。制备的聚硒吩膜柔韧、致密、均一，能被切割成任意形状。同时研究表明，硒原子对共轭聚合物链的骨架产生明显影响使得聚合物的热稳定性显著提高。 2、首次在三氟化硼乙醚溶液中进行了荧蒽单体的电化学聚合，并成功制备了高性能的聚荧蒽膜，其电导率约为10^-2S cm^-1。制备的聚荧蒽膜在浓硫酸中表现出较好的氧化还原活性和较高的稳定性。聚荧蒽能部分溶解于极性有机溶剂，其溶解部分有较强的荧光。通过量化计算和¹H-NMR光谱分析，表明荧蒽在三氟化硼乙醚中电化学聚合时，聚合可能发生在荧蒽环的C₃、C₄、C₁₃和C₁₄位。 3、首次在三氟化硼乙醚溶液中合成了5位卤素取代聚吲哚膜，在该体系中，5位卤素取代吲哚的氧化电位均低于相同条件下在乙腈体系中的氧化电位，吲哚和5位卤素取代吲哚的氧化电位变化都呈现出一定的规律性，即E_Fin＞E_Clin＞E_Brin＞Eindok。通过红外光谱和’H-NMR光谱分析，表明5位卤素取代吲哚在三氟化硼乙醚中电化学聚合时，聚合发生在吲哚环的C₂和C₃位。更多还原

【Abstract】 Electrochemical polymerization had been proved to be one of the most useful approaches for conducting polymer synthesis with several advantages. This dissertation focused on the electrosyntheses and the characterizations of high-quality conducting polymers in pure boron trifluoride diethyl etherate （BFEE）, such as polyselenophene, polyfluoranthene, poly （5-fuoroindole）, poly （5-chloroindole） and poly （5-bromoindole）. The interactions between the middle strong Lewis acid, BFEE, and the aromatic monomers lower their oxidation potentials, which facilitates the formation of high quality polymer films.1. High-quality free-standing polyselenophene films with conductivity of 2.8×10^-1 S cm^-1 were synthesized electrochemically by direct oxidation of selenophene in pure BFEE for the first time. The oxidation potential of selenophene in this medium was measured to be only 1.23 V vs. SCE, which was much lower than that in acetonitrile + 0.1 BU4NBF4 （1.83 V vs. SCE）. PSe has better thermal stability than polythiophene, wich can be inferred that the more polarizable and larger selenium atom presents a notable effect on increasing the thermal stability.2. High-quality polyfluoranthene films with electrical conductivity of 10^-2 S cm^-1, were synthesized electrochemically by direct anodic oxidation of fluoranthene in BFEE for the first time. Polyfluoranthene films obtained from this medium showed good redox activity and stability even in concentrated sulfuric acid. The polymer synthesized in this medium was partially soluble in polar organic solvents. The soluble part of polymer had a strong fluorescence. Quantum chemistry calculations and ¹H NMR spectra showed that the polymer chains were grown via the coupling of the monomer at C₃, C₄, C₁₃, C₁₄ positions.更多还原