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Direct Introduction of Hetero Atoms into Hydrocarbons in Plasmas

将杂原子直接引入等离子体中的碳氢化合物

基本信息

批准号：
07651036
负责人：
TEZUKA Meguru
金额：
$ 1.28万
依托单位：
Saitama Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651036/
关键词：
Plasma Aromatic Hydrocarbon Hetero Atom Introduction Hydroxylation Cyanation Glow Discharge Electrolysis

项目摘要

In this study, The creation super-reactive species which might be formrd by conventional chemical methods and its introduction into hydrocarbons has been aimed. Special attention has been paied not only to gaseous plasma reactions but also solution-phase organic reactions induced by plasma, namely glow discharge electrolysis (gde).In 1995, the oxidation of aromatic hydrocarbons with oxygen in a radio-frequency plasma was examined. When a variety of alkylbenzenes were fed into the gaseous plasma, the hydroxylation of benzene rings competed with the oxidation of alkylgroups. On the other hand, the olefinic double bonds were preferentially oxidized to the corresponding epoxides.In 1996, the oxidative degradation of organic substances dissolved in an aqueous solution was conducted by means of gde. Thus, phenols was eventually decomposed to carbon dioxides and water. As the intermediate products, hydroquinone and catechol were formed. Successively, they were oxidized to pyrogallol and hydroxyhydroquinone. The cleavage of benzene nucleus subsequently occurred to yield a diversity of carboxylic acids such as oxalic or formic acids. It was assumed that hydroxyl radical resulting from the dissociation of water molecule should be responsible for the pxidation.the application of gde methods to organic solvent system was attempted. In the gde of acetonitrile, propionitrile, acrylonitrile and succinonitrile were obtained as major products in the solution-phase. The reaction scheme involving the ionic species, probably acetonitrile cation, which could be generated in the discharge zone and might ruch into the solution surface layr to break up several solvent molecules, was proposed. The resulting radical, that is methyl and cyano radicals, should be mutually recombined to give rise to the above-mentioned products.

在这项研究中，目的是创造可通过常规化学方法形成的超反应物质并将其引入碳氢化合物中。人们不仅对气态等离子体反应给予了特别关注，而且还对等离子体引起的液相有机反应，即辉光放电电解（GDE）给予了特别关注。1995年，研究了射频等离子体中芳香烃与氧的氧化反应。当多种烷基苯被送入气态等离子体时，苯环的羟基化与烷基的氧化竞争。另一方面，烯属双键优先被氧化成相应的环氧化物。1996年，利用gde对溶解在水溶液中的有机物进行了氧化降解。因此，酚类最终分解为二氧化碳和水。作为中间产物，形成对苯二酚和儿茶酚。随后，它们被氧化成连苯三酚和羟基氢醌。随后苯核发生裂解，产生多种羧酸，例如草酸或甲酸。推测水分子解离产生的羟基自由基应负责氧化反应。尝试了GDE方法在有机溶剂体系中的应用。在乙腈反应中，在溶液相中得到主要产物丙腈、丙烯腈和丁二腈。提出了涉及离子物质（可能是乙腈阳离子）的反应方案，该离子物质可能在放电区产生并可能冲入溶液表面层以分解多个溶剂分子。所得自由基，即甲基和氰基，应相互重新结合以产生上述产物。