摘要
本文研究了铜（Ⅱ）盐催化氯代苯酚的聚合反应，利用元素分析、ＩＲ（红外）和ＮＭＲ（核磁共振）对聚合物的结构进行了鉴定．分离出了聚合过程中所形成的氯代苯氧——铜（Ⅱ）配合物中间体，并利用元素分析、ＥＳＲ（电子自旋共振）研究了该配合物中间体．该配合物中间体在苯中回流得到相应的聚合物．ＥＳＲ研究该配合物中间体发现在空温下有苯氧自由基的存在，并在１２０℃热分解过程中发现苯氧自由基的ＥＳＲ谱随着规定时间的延长强度在下降，由此提出了铜（Ⅱ）盐催化由氯代苯氧—铜（Ⅱ）配合物中间体生成相应聚合物的单电子转移历程。
Abstract The copper(Ⅱ)-catalyzed polymerization of 2,4,6-trichlorophenol was studied. Its polymer's structure was confirmed by elementary analysis, IR (infrared) and NMR (Nuclear Magnetic Resonance). The 2,4,6-trichloro-phenoxo-copper (Ⅱ) complex intermediate was isolated. The elementary analysis, ESR (Electron Spin Resonance) spectra of the copper (Ⅱ) complex was discussed in relation to its structure. Decomposition of the copper (Ⅱ) complex in refluxing benzene yielded poly (dichlorophenylene oxide). ESR measurements on the copper (Ⅱ) complex in the solid state at 120℃ indicated that the phenoxy radical was generated during the period of decomposition and the intensity of the ESR spectra based on copper (Ⅱ) ion decreased with the measurement time. Single electron transfer reaction mechanism was proposed for the copper (Ⅱ)-catalyzed polymerization through the 2,4,6-trichlorophenoxo-copper (Ⅱ) complex intermediate.
