Study on Elementary Reaction for Plasma Polymerization Using in situ Mass Spectroscopy

在等离子体聚合物中引入官能团是向等离子体聚合物中添加贵官能团所必需的。在这项研究中，一个离子交换能力的聚合物作为血浆聚合物的功能，从现场质谱和分子轨道计算的结果，在血浆中的各种活性中间体进行了讨论。同时将用于形成聚合物主链和添加官能团的两种单体引入反应室中。以二氟甲苯和二氯甲苯为单体进行官能团的加成反应。两种化合物的化学结构非常相似。然而，理论分子轨道计算提供了这些起始单体在等离子体中的稳定活性物质的差异。在氟化物的情况下，可以在等离子体聚合物中引入砜基。在氯化物的情况下，砜基可以被电子攻击，形成包括S元素的其他化合物（砜是引入磺酸基所希望的，因为它可以通过碱性溶液的水解容易地变成磺酸基）。当使用这些起始单体时，使用活性物种的原位质谱，显示出与分子轨道计算的预期结果良好对应的结果。在优化条件下制备的等离子体聚合物薄膜的离子交换能力为0.99的高阳离子迁移数和10 μ S·cm ~（-1）的高离子电导率<-4><-1>。等离子体聚合物薄膜如此之薄，以至于实际电阻率与商业化的阳离子交换膜（Nafion 117）相当。

The introduction of functional group into plasma polymer is necessary for the addition of a noble function to plasma polymer. In this study, an ion exchange ability of polymer was discussed as the function of plasma polymer from the results of in situ Mass spectroscopy and molecular orbital calculation for various active intermediates in plasma. Both monomers for the formation of polymer backbone and the addition of functional group were introduced into a reaction chamber simultaneously. Benzenefluoride and benzenechloride were used as a monomer for the addition of functional group. The chemical structures of both compounds were very similar each other. However, the theoretical molecular orbital calculation provides the difference in the stable active species of these starting monomers in plasma. In the case of fluoride, sulfone group may be introduced in the plasma polymer. In the case of chloride, sulfone group may be attacked by electron to form other compounds including S element (Sulfone is desirable to the introduction of sulfonic acid group, because it can be easily changed to sulfonic acid group by hydrolysis with alkaline solution.) The in situ mass spectroscopy for the active species when using these starting monomers are used, shows the well corresponding result to the expectation from the molecular orbital calculation. The ion exchange ability of the plasma polymer thin film prepared from fluoride under optimized conditions has a high cationic transference number of 0.99 and a high ionic conductivity of 10^<-4>S cm^<-1>. The plasma polymer thin film was so thin that the practical resistivity was comparable with the commercialized cation exchange membrane (Nafion 117) .