Synthesis of Novel Functional Conductive Polymers in Supercritical Carbon Dioxide and their Properties

在这一工作中，我们研究了在同源超临界条件下的导电聚合物的电化学合成。几个因素对暴露的聚合物薄膜的压力、相位行为和质量转移过程的影响，Thiophene被选择为超临界碳二氧化物中电泳的模型单体（scCO_2）。The homogeneous supercritical state被确认为通过一个高压力细胞的观察阶段行为的观察。在scCO_2中合成三苯的诱导聚合物薄膜被表征为循环电压计、SEM、激光显微镜、AFM和四点探测器的诱导性。该系统中的电影的粗糙度被CO_2的另一个附加物降解了。这一结果提出了一个低可见度的scCO_2发挥了一个重要的作用，以提高解决率的转移率。在同源scCO_2/丙酮腈（AN）系统中准备的电影的粗糙度与t相比 ... More 在二氯甲烷中准备的帽子。电影的缓慢增长和单体似乎有很高的扩散率被认为是平滑和平坦的电影形成的。其他诱导性聚合物、聚苯胺和聚吡咯类在同源scCO_2/ AN系统中成功地合成。此电聚合化系统已扩展到作为过氧化物传感器的应用的硫酰卟啉（H23 ThTETP）的聚合化。H23 ThTEtP的结果电影使用SEM、激光显微镜和AFM进行了表征。它被证实是，在scCO_2提供的平板、光滑和高度密集的活性站点比在有机溶剂中的一个电聚合化了，该聚合膜被用作一个电催化剂应用于超氧化物传感器。催化剂显示了氧化的选择性和活动·显示了当前和02之间的线性关系·集中，揭示了02·体内定量分析的可能性。催化剂显示出比有机溶剂中的一种电聚合物更高的敏感性。Less（低）

In this work, we have investigated the electrochemical synthesis of conductive polymers in homogenous supercritical condition. The effects of several factors such as pressure, phase behavior and mass transfer process for the obtained polymer film were examined.Thiophene was chosen as a model monomer to electropolymerize in supercritical carbon dioxide (scCO_2). The homogeneous supercritical state was confirmed by the observation of the phase behavior through a high-pressure cell with a viewing window. The conductive polymer film of thiophene synthesized in scCO_2 was characterized with cyclic voltammetry, SEM, Laser microscopy, AFM and four-point probe conductivity. The roughness of the film in that system was decreased with the further addition of CO_2. This result suggested that the low viscosity of scCO_2 play an important role in improving the transfer rate of solvent. The roughness of the film prepared in the homogeneous scCO_2/ acetonitrile (AN) system was reduced compared with t … More hat prepared in dichloromethane. The slow growth of the film and the high diffusion rate of the monomer seemed to account for the smooth and flat film formation. Other conductive polymers, polyaniline and polypyrrole, were successfully synthesized in a homogeneous scCO_2/ AN system.This electropolymerization system was extended to the polymerization of thienylporphyrin (H23ThTEtP) for the application as a superoxide sensor. The resulting film of H23ThTEtP was characterized using SEM, laser microscopy and AFM. It was revealed that the electropolymerized film in scCO_2 provided flatter, smoother and higher densified active sites than the one electropolymerized in organic solvent.The polymerized film as an electrocatalyst was applied to a superoxide sensor. The catalyst displayed selectivity and activity for the oxidation of 02・and showed a linear relationship between current and 02・concentration, which revealed the possibility of quantitative analysis of 02・in vivo. The catalyst showed higher sensitivity than the one electropolymerized in organic solvent. Less