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Photoreactions of pi-Electron-System-Substituted Disilanes and their Application to Photoactive Polymers

π电子体系取代乙硅烷的光反应及其在光活性聚合物中的应用

基本信息

批准号：
04555209
负责人：
ISHIKAWA Mitsuo
金额：
$ 7.55万
依托单位：
HIROSHIMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

项目摘要

Alternating polymers composed of a disilanylene group and pi-electron system, poly[(disilanylene)phenylenes], poly[(disilanylene)naphthylenes], poly[(disilanylene)thienylenes], poly[(disilanylene)dithienylenes], poly[(disilanylene)butenyne-1, 4-diyls], and poly[(disilanylene)ethynylenes] were synthesized and their photochemical properties were investigated.These polymers are soluble in common organic solvents and can be casted to thin solid films by spin-coating. UV-irradiation of the films in air caused the cleavage of the Si-Si bonds leading to the formation of Si-O bonds. Photolysis of the polymers in solution was also investigated. Thus, when these polymers were photolyzed in the presence or absence of a trapping agent in benzene, products which can be best explained by assuming the silyl radicals formed by the homolytic scission of an Si-Si bond were obtained. The silyl radicals thus formed undergo two different reactions under the conditions used. One involves the disproportionation reaction leading to the formation of a silene and hydrosilane, while the other comprises a cross-linking addition reaction across the pi-electron system. In these photoreactions, it was found that introduction of an alkyl group on the silicon atom in the polymer, main chain is favorable for the cross-linking reaction, while replacement of the alkyl group by an aryl group facilitates the disproportionation reaction. It was also found that the extension of the pi-electron system in the polymer chain results in the decrease of the photoactivities of the present polymers.In order to learn more about the photochemical properties of these polymers, we prepared disilanylene-phenylene oligomers as model compounds and investigated their photochemical behavior.

由亚二硅烷基和π电子系统组成的交替聚合物，聚[（二硅亚基）亚苯基]、聚[（二硅亚基）亚萘基]、聚[（二硅亚基）噻吩亚基]，聚[（二亚硅烷基）二噻吩亚基]，聚[（亚二硅烷基）丁烯炔-1，4-二基]，聚[（二亚硅基）亚乙炔基]这些聚合物可溶于普通有机溶剂，可浇铸成固体薄膜通过旋涂。在空气中紫外光照射导致Si-Si键断裂，形成Si-O键。还研究了聚合物在溶液中的光解。因此，当这些聚合物在存在或不存在捕集剂的情况下在苯中光解时，可以通过假设由Si-Si键的均裂形成的甲硅烷基自由基得到最好的解释的产物。由此形成的甲硅烷基在所用条件下经历两种不同的反应。一个涉及导致形成硅烯和氢硅烷的交联反应，而另一个包括跨π电子系统的交联加成反应。在这些光反应中，发现在聚合物主链中的硅原子上引入烷基有利于交联反应，而用芳基取代烷基有利于交联反应。为了进一步了解这些聚合物的光化学性质，我们制备了二硅亚苯基齐聚物作为模型化合物，研究了它们的光化学行为。