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Synthesis and Properties of One-Dimensional Conjugated Polymer (Carbyne).

一维共轭聚合物（卡宾）的合成与性能。

基本信息

批准号：
62470099
负责人：
SHIRAKAWA Hideki
金额：
$ 3.2万
依托单位：
Institute of Materials Science, University of Tsukuba
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470099/
关键词：
Carbyne Conjugated Triple Bonds Conducting Polymers Doping Polyyne 塩素化ポリアセチレン

项目摘要

Novel synthetic method of one-dimensional conjugated polyyne so-called carbyne is investigated. Synthetic strategy employed is dehydrochlorinations of stereospecifically chlorinated polyacetylene, (CHCl)_x which is synthesized through prolonged FeCl_3-doping and polyvinylidene chloride. In the dehydrochlorinations using DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) as a strong organic base, usage of a polar solvent such as DMSO or DMF is essential. From spectroscopic measurements such as ultraviolet and visible absorption, infrared absorption, and Raman scattering, it is elucidated that the dehydrochlorination proceeds via two steps of trans elimination of HCl to yield carbyne but not cumulene, and that carbynes formed are composed of polyyne segments with various chain lengths of carbon-carbon triple bonding -(C C)_n-ranging n = 10 to 40. It is also elucidated that the carbyne thus synthesized is too labile to exist without an oxygenation and a cross-linking of the t riple bonds in air and at ambient temperature.

研究了一维共轭多炔（简称碳炔）的合成新方法。采用的合成策略是将FeCl_3长时间掺杂合成的聚乙炔（CHCl）_x与聚偏二氯乙烯（PVDF）进行脱氯化氢反应。在使用DBU（1，8-二氮杂双环[5，4，0]十一碳-7-烯）作为强有机碱的脱氯化氢中，使用极性溶剂如DMSO或DMF是必要的。通过紫外、可见吸收、红外吸收和拉曼散射等光谱测量，阐明了脱氯化氢反应是通过HCl的反式消除两步反应生成碳炔而不是枯烯，生成的碳炔是由不同碳-碳三键（C C）n-链长（n = 10 ~ 40）的多炔链段组成的.本文还阐明了这样合成的碳炔在空气中和室温下不经氧化和三键交联就不稳定。