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

原位质谱法研究等离子体聚合基元反应

基本信息

批准号：
05650825
负责人：
TAKEHARA Zen-ichiro
金额：
$ 1.41万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

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) .

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贱功能的必要条件。本文从等离子体中各种活性中间体的原位质谱和分子轨道计算结果出发，讨论了聚合物的离子交换能力作为等离子体聚合物的函数。在反应室中同时引入了用于聚合物主链形成和官能团加成的两种单体。以氟化苯和氯化苯为单体加成官能团。这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。在氟的情况下，可在等离子体聚合物中引入砜基。以氯化物为例，砜基可能会被电子攻击，形成包括S元素在内的其他化合物（砜是需要引入磺酸基的，因为它可以很容易地被碱性溶液水解为磺酸基）。用这些起始单体对活性组分进行了原位质谱分析，结果与分子轨道计算的预期结果吻合较好。在优化条件下制备的氟离子等离子体聚合物薄膜离子交换能力高，阳离子转移数为0.99，离子电导率为10^<-4>S cm^<-1>。等离子体聚合物薄膜非常薄，其实际电阻率与商品化阳离子交换膜相当（Nafion 117）。