Structural Effects of Ion Transport in Macromolecules

利用物质特有的分子组装是开发新材料的基本方法，但也是最有效的方法。这项研究旨在探索离子在大分子中传输的结构效应，特别是在玻璃化转变温度以上的物理或化学交联聚合物中，这是一种独特的、动态的大分子组装。本研究的重要成果如下：1.离子导电聚合物表征方法的发展利用复阻抗法和恒电位极化法相结合的方法，以及利用具有超微电极的固态三电极电池，成功地估算了离子导电聚合物的离子输运数和电位窗口。大分子离子输运的结构和动力学效应已经证明，大分子…中离子输运的最具特征的行为分子内溶剂化是聚合物链中相邻极性基团与离子协同溶剂化(分子内溶剂化)所导致的载流子生成，以及与溶剂化有关的高分子链的链段运动与离子传输的完全耦合。用几种基于聚醚网络和聚谷氨酸的模型聚合物偏离了这些重要的结果。通过在聚醚氨酯中引入-SO^-_Li^+基团，合成了输运数为1的锂离子导电聚合物。离子导电聚合物作为反应介质的功能离子导电聚合物除了具有离子导电性能外，还具有通过简单的溶解或化学修饰来结合氧化还原活性分子的有趣性质。这两种性质的结合导致了一种想法，即离子导电聚合物可以用作电化学合成和电化学反应的固态溶剂。为了证明这一想法，我们对吡咯进行了电聚合，得到了由电子/离子导体组成的氧化还原活性双层膜。研究还发现，在没有任何低分子量溶剂的情况下，二茂铁在离子导电聚合物中发生可逆氧化还原反应。较少

It is a fundamental, but a most powerful methodology for developing new materials to utilize characteristic molecular assembly of substances. This research has been aimed at exploring structural effects of ion transport in macromolecules, especially in physically or chemically crosslinked polymers above their glass transition temperatures, which are unique and dynamic molecular assembly of macromolecules. The important results of this research are as follows:1. Development of Methodology for Characterizing Ion-Conducting Polymers Ionic transport number and potential window of ion-conducting polymers have been successfully allowed to be estimated by the combination of complex impedance and potentiostatic polarization methods and by the utilization of solid-state-three-electrode-cells having ultra-microelectrodes, respectively.2. Structural and Dynamic Effects of Ion Transport in Macromolecules It has been demonstrated that the most characteristic behavior of ion transport in macromolecu … More les is the carrier generation caused by cooperative solvation of neighboring polar groups in polymer chains to ions (intramolecular solvation) and the completely coupled ionic transport with segmental motion of the polymer chains that are responsible to the solvation. These important results were deviated by using several model polymers based on polyether networks and polyglutamates. Li^+ conducting polymers having its transport number of unity have been gynthesized by introducing -SO^-_Li^+ groups into polyether urethanes.3. Function of Ion-Conducting Polymers as Reaction Media Ion-conducting polymers have interesting property to incorporate redox active molecules by simple dissolution or chemical modification, in addition to ion-conducting property. Combination of these two properties has led to an idea that ion-conducting polymers can be used as solid state solvents for electrochemidal syntheses and electrochemical reactions. In order to demonstrate this idea, electropolymerization of pyrrole has been carried out, resulting in redox active bilayers consisting of electron/ion conductors. It is also found that ferrocene dissolved in ion-conducting polymers undergoes a reversible redox reaction in the absence, of any low-molecular-weight solvent. Less