邻氨基酚与邻苯二胺共聚的原位紫外-可见光谱电化学研究  

In Situ UV-Vis Spectroelectrochemical Study on Copolymerization of o-Aminophenol and o-Phenylenediamine

作　　者：徐文茹[1] 张雷[1] 

机构地区：[1]上海师范大学生命与环境科学学院化学化工系,上海200234

出　　处：《分析测试学报》2014年第12期1334-1341,共8页Journal of Instrumental Analysis

基　　金：上海市教育科学研究项目(B-13034)

摘　　要：运用循环伏安法(CV)和原位紫外-可见光谱电化学法分别研究了邻氨基酚(OAP)和邻苯二胺(OPD)在1 mol/L HCl溶液中单独聚合及二者共聚的电化学过程。OAP和OPD单独聚合及二者共聚时呈现出的不同电化学行为表明OAP和OPD发生了共聚反应。原位紫外-可见光谱研究表明,在共聚过程中,OAP和OPD首先分别被氧化生成其相应的阳离子自由基,然后,OAP和OPD的阳离子自由基与溶液中的OPD和OAP单体或其阳离子自由基发生交互反应生成类苯胺和类吩嗪结构的二聚物/低聚物中间体,生成的中间体继续发生耦合反应生成OAP和OPD的共聚物,呈现出两个波长分别位于477 nm和419 nm处的吸收峰。并用傅立叶变换红外光谱(FT-IR)表征了共聚物的生成。进一步研究发现,OAP和OPD的共聚过程与溶液中OAP和OPD单体的浓度比有关。The copolymerization of o-aminophenol（OAP） and o-phenylenediamine （OPD） was studied by using in situ ultraviolet-visible （UV-Vis） spectroelectrochemical and cyclic voltammetric techniques.The different voltammetric characteristics in homopolymerization and copolymerization processes exhibited the occurrence of the copolymerization between OAP and OPD in 1 mol/L HCl solution.The in situ UV-Vis spectra showed that,during the copolymerization of OAP and OPD,OAP and OPD were firstly oxidized to generate their cation radicals,then the new-formed dimers/oligomers intermediates：phenazine-type structure and PANI-like backbone structure were formed by the cross-reaction of the cation radicals of OAP and OPD with the OAP and OPD monomers or their cation radicals in solution.The dimers/oligomers intermediates continued to react to form copolymer,showing two absorption peaks located at 477 nm and 419 nm,respectively.Fourier transform infrared Spectroscopy（FF-IR） was used to characterize the formation of the copolymer of OAP and OPD.Further studies showed the difference between the copolymerization of OAP and OPD with different concentration ratios,indicating the dependence of the copolymerization on the concentrations of OAP and OPD.

关 键 词：邻氨基酚 邻苯二胺 共聚 原位紫外-可见光谱 

分 类 号：O561.3[理学—原子与分子物理] O623.732[理学—物理]