新型偶氮喹啉聚合物的合成及其光化学性质

Vitalii SMOKAL, Dmytro KHOMENKO, Roman DOROSHCHUK, Oksana KHARCHENKO
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引用次数: 0

摘要

现代技术的发展不断要求寻求新的低成本、高效的材料,并建立应用这些材料的新技术方法。一方面合成具有预测和预期性能的聚合物,另一方面利用聚合物中光活性片段相互作用的特定特征,为基于这些聚合物的新材料的应用开辟了新的前景。具有不同活性官能团的侧链甲基丙烯酸聚合物在光电子学、非线性光学、光存储材料、生物化学和医学等领域得到了广泛的研究和应用。本文主要研究了含偶氮苯基的新型甲基丙烯酸单体及其与甲基丙烯酸甲酯(MMA)共聚物的合成。本文首次报道了侧链上含有6-偶氮苯基喹啉片段的甲基丙烯酸聚合物的合成及其光化学性质。此外,本文还详细介绍了以新型偶氮化合物为基础的单体和聚合物的合成特点。采用紫外可见分光光度法研究了新型偶氮片段喹啉聚合物在四氢呋喃溶液中的吸收光谱特性。所有聚合物在300-375 nm范围内表现出由π-π*电子跃迁引起的强吸收带,在400-490 nm范围内表现出由n-π*电子跃迁引起的弱吸收带。偶氮-喹啉聚合物溶液中喹啉分子的给电子取代基和吸电子取代基引起π-π*吸收带的显色位移,这与本文的研究结果一致。我们发现,红移随取代基给电子强度的增加而增加,也随取代基吸电子强度的增加而增加。基于所获得的结果,我们可以假设,偶氮碎片聚合物的辐照导致光致反顺异构化。 从所得的结果和所提出的结果可以得出结论,具有偶氮片段的新型喹啉聚合物可以被认为是在一定波长范围内要求光敏性的应用的有前途的材料。
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SYNTHESIS AND PHOTOCHEMICAL PROPERTIES OF NOVEL AZOQUINOLINE CONTAINING POLYMERS
The development of modern technologies are constantly requires seeking new low-cost, efficient materials and establish new technical methods for application these materials. Synthesis of polymers with predicted and expected properties on the one hand and using specific features of interaction light with photoactive fragments in polymers, on the other hand, opens new prospects of application for new materials based on these polymers. The side chain methacrylic polymers with different active functional group have been well studied and widely applied in many fields, such as optoelectronics, nonlinear optics, optical storage materials, biochemicals, and medicine. The present work focused on synthesis new azostyrylcontaining methacrylic monomers and copolymers with methylmetacrylate (MMA) based on these monomers. The pre­sent study is a first reported notice of the synthesis and photochemical properties of methacrylic polymers with 6-azo-phenylquinoline frag­ments in side chain. Moreover in this work the features of syntheses have been described in detail for monomers and polymers based on new azocompounds. Absorption spectroscopic properties for new quinoline polymers with azo fragment were investigated with UV-Vi­sible spectrophotometry in THF solutions. All studi­ed polymers show a strong absorption band in the range of 300–375 nm resulting from π-π* electronic transition and a weak absorption band in the range of 400–490 nm assigned to n-π* transitions. Electron donating and electron withdrawing substituents at quinoline moity of azo-quinoline polymer solutions lead to bathochromic shift of the π-π*absorption band which agrees well with the result of work. We found that this red-shift increases with an increase of electron donating strength of the substituent as well as with an increase of electron withdrawing strength of the substituent. Based on of the result achieved we can suppose that irradiation of polymers with azo fragment lead to photoinduced trans-cis-isomerization. From the obtained and presented results one can conclude that novel quinoline polymers with azo fragment can be considered as promising materials for applications requiring photosensitivity in certain of range of wavelength.
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