【作者】 任红霞；

【导师】 王云普；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2004， 博士

【摘要】 本论文由以下五部分组成： 第一部分：文献综述 回顾了氮杂环高分子的发展历史，重点对金属卟啉的催化性能进行了阐述，尤其突出在界面上的自组装过程，分析了基于分子自组装膜表面的化学反应及其特性，希望能对利用分子自组装技术进行各种功能材料尤其是界面材料的设计和构筑有一定的启发意义。 第二部分：高分子键联金属卟啉的合成及表征 以合成的小分子单羟基卟啉为母体，引入性质稳定的高分子化合物氯甲基化聚苯乙烯，并在此基础上再进行修饰，得到不同的高分子键联金属卟啉。为更好地进行电化学研究，通过改变高分子链得到可溶性的高分子卟啉，从而将其应用于自组装技术中。红外光谱、紫外光谱、核磁共振谱、分子量测定、元素分析、扫描电镜、金属含量分析、X-射线光电子能谱等表征结果确认了化合物设计与合成的正确性。 第三部分：高分子键联金属卟啉的电化学性质 以高分子键联金属卟啉为修饰剂制备的化学修饰碳糊电极作为工作电极，研究了在铁氰化钾溶液中电极的电化学行为，以及在柠檬酸—磷酸氢二钠缓冲溶液中对抗坏血酸的电催化氧化作用。 第四部分：巯基高分子卟啉自组装膜的表征及对氧的催化还原 利用扫描电化学显微镜和电化学方法对尾式巯基高分子卟啉的自组装修饰金电极进行了表征，同时研究了它的制备和对分子氧的电催化还原特性。 第五部分：高分子键联金属卟啉催化氧化环己烯反应 研究了键联聚乙二醇高分子担载锰卟啉以及钴卟啉的合成，并考查了它们在环己烯氧化过程中的催化性能。结果表明：金属卟啉和高分子键联后稳定性增加，也是烯烃氧化反应的一种有效催化剂，且催化性能随着金属离子的不同有所选择。更多还原

【Abstract】 This thesis is composed of five parts, which are as follows:Part 1: ReviewIt reviewed the progress of nitrogen heterocyclic polymers, especially the catalytic performance of metalloporphyrins. Their self-assembled process on interface was mainly discussed. Then the reaction on surface and the properties of self-assembled monolayers were also expatiated. It is hoped that self-assembled monolayers technology has developmental purpose in designing and constructing different functional materials, especially in interface materials.Part 2: Synthesis of Polymer-Bounded Metalloporphyrins Polymer-bounded metalloporphyrins were synthesized by the reaction of chloromethyl polystyrene and 5-(p-hydroxyphenyl)-10,15,20-triphenylporphyrin, which was basic. However, the soluble polymer porphyrin gotten by changing the structure of polymer chains was applied to self-assembled technique. They were characterized by FT-IR, ICP, UV/vis, GPC, 1HNMR, SEM, XPS, element analysis, etc.Part 3: Electrochemical Behavior of Polymer-Bounded Metalloporphyrins Polymer-bounded metalloporphyrins was intermingled into the carbon pastes to make carbon paste electrodes as a working electrode. Its electrochemical behavior in potassium ferricyanide solution and electrocatalytic oxidation for ascorbic acid in citric acid-disodium hydrogen phosphate buffer solution was investigated.Part 4: The Characterization of Mercapto Polymer Porphyrin Self-Assembled Monolayers on Gold Electrode and Electrocatalytic Dioxygen ReductionMercapto polymer porphyrin self-assembled monolayers was characterized by scanning electrochemical microscope(SECM) and electrochemistry technique and theelectrocatalytic reduction of dioxygen was investigated by cyclic voltammetry at a gold electrode adsorbed with mercapto polymer porphyrin in dioxygen-saturated aqueous solutions of various pH.Part 5: Catalytic Performance of Polymer-Bounded Metalloporphyrins on the Oxidation of CyclohexeneSynthesis and catalytic performance of polymer-bounded metalloporphyrins bearing polyglycol chains were studied. The influence of additive and phase transfer catalysts on the oxidation of cyclohexene catalyzed by those catalysts has also been investigated. The experimental results show that manganese( II) and cobalt( II) porphyrins bound to chloromethylated polystyrene which bears some polyglycol chains are efficient catalysts for the oxidation of cyclohexene.更多还原