Abstract

Initial stages of aniline galvanostatic polymerization at platinum electrode in aqueous solutions of poly-2-acrylamido-2-methyl-1-propansulfonic acid and polystyrenesulfonic acid are studied by the method of Raman spectroelectrochemistry. A laser with wavelength of 532 nm excited the Raman scattering. The very presence of intermolecular associates able to luminescence in the polyacid solution (in the case of polystyrenesulfonic acid) was shown to result in the Raman-spectrometer photodetector overload if normal incidence of laser beam at the electrode (the angle 0°) was used. The Raman-spectrometer photodetector overload can be avoided by the varying of the incidence angle over the 0°–20° range, even without using other techniques (leading to a decrease in the reliability of the studied Raman band registration, such as the lowering of the integration time, intensity or energy of the excitation). Comparative study of aniline electropolymerization in the presence of poly-2-acrylamido-2-methyl-1-propansulfonic acid, polystyrenesulfonic acid, and HCl revealed some characteristic bands in the Raman spectra of the polyaniline–polyacid complexes in the Raman frequency range from 2000 to 3000 сm^–1; these bands relate to the polyacid’s backbone and are absent in the Raman spectra of the polyaniline–HCl film. The dynamics of changes in the contribution to the integral Raman spectrum of the band of radical-cations (1330–1350 сm^–1) characterizing the highly conductive emeraldine form of polyaniline was compared for the polymerization media. In the course of the electrosynthesis it was found, that the accumulation rate of these species in the film decreased in the series poly-2-acrylamido-2-methyl-1-propansulfonic acid > HCl > polystyrenesulfonic acid.

中文翻译：

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在聚合物酸介质中研究聚苯胺电合成时应用拉曼光谱电化学方法的一些特殊特征

抽象的

用拉曼光谱电化学方法研究了聚-2-丙烯酰胺基-2-甲基-1-丙磺酸和聚苯乙烯磺酸水溶液中铂电极上苯胺恒电流聚合的初始阶段。波长为532 nm的激光激发了拉曼散射。如果使用激光束在电极上的垂直入射（角度为0°），则在多酸溶液中（如果是聚苯乙烯磺酸的话）能够发光的分子间缔合体的存在会导致拉曼光谱仪光电探测器过载。即使不使用其他技术，也可以通过在0°–20°范围内改变入射角来避免拉曼光谱仪光电探测器过载（导致研究的拉曼谱带配准的可靠​​性降低，例如降低积分时间，降低激发强度或能量）。在聚-2-丙烯酰胺基-2-甲基-1-丙磺酸，聚苯乙烯磺酸和HCl存在下对苯胺电聚合的比较研究显示，从2000年开始，聚苯胺-聚酸配合物的拉曼光谱中有一些特征谱带到3000сm^–1 ; 这些谱带与多元酸的主链有关，在聚苯胺-HCl膜的拉曼光谱中不存在。对于聚合介质，比较了表征高导电性翡翠形式聚苯胺的自由基阳离子带（1330–1350сm– ¹）对积分拉曼光谱的贡献变化的动力学。在电合成的过程中，发现在聚-2-丙烯酰胺基-2-甲基-1-丙磺酸> HCl>聚苯乙烯磺酸系列中，这些物质在膜中的积累速率降低。