双卤代—二（3, 4-乙烯二氧噻吩）苯甲烷的光聚合研究

发布时间：2018-12-23 13:22

【摘要】：自从1977年发现导电聚乙炔以来,共轭聚合物逐渐成为现代材料学研究的热点之一。得益于其半导体特性,以及能级和能带可控的特点,共轭聚合物在现代有机电子学中得到广泛应用,取代无机半导体应用于场效应晶体管,聚合物太阳能电池,电致发光器件,电致变色器件等领域。在过去的十多年里,共轭聚合物传感器受到研究者的关注,开发出众多检测溶液中阴、阳离子的传感器,利用被测分子与共轭聚合物功能化的支链发生配位及分子间相互作用,对聚合物的能级产生微扰,改变聚合物的吸收和荧光光谱,传递信号,完成检测。光聚合反应属于自由基聚合的一种,利用光照产生活性自由基与单体反应,发生聚合。光引发聚合动力学已经十分清楚,反应广泛应用于涂料、油墨等领域。对于有限的固态光聚合反应(拓扑聚合)体系的聚合机理也已经研究比较透彻。噻吩的卤代衍生物固态光聚合反应报道较少,对反应过程的研究也比较少。一般认为这类反应通过光照断裂碳卤键,产生自由基引发反应。本论文合成了两个类三苯胺结构的双卤代双(3,4-乙烯二氧噻吩基)苯甲烷单体并光照聚合,发现:不同的取代卤素产生了不同的聚合物红外和紫外光谱。中性聚合物可以用作溴和碘传感器,检出限为50ppm,并且聚合物在高浓度卤素溶液下不稳定。此外,通过聚合反应动力学研究表明,聚合反应级数对单体为1/2级,两个单体在254 nm紫外光下的表观反应速率常数非常接近,即两个单体具有相同的反应速率。
[Abstract]:Since the discovery of conducting polyacetylene in 1977, conjugated polymers have become one of the hotspots in modern materials. Thanks to their semiconductor properties and controllable energy levels and band, conjugated polymers have been widely used in modern organic electronics, replacing inorganic semiconductors for field effect transistors, polymer solar cells, electroluminescent devices, Electrochromic devices and other fields. In the past decade or so, conjugated polymer sensors have attracted the attention of researchers. Many sensors for the detection of anions and cations in solution have been developed to coordinate and interact with the functionalized branched chains of conjugated polymers. The energy level of the polymer is disturbed, the absorption and fluorescence spectra of the polymer are changed, the signal is transmitted and the detection is completed. Photopolymerization is a kind of radical polymerization. The reactive free radical is produced by light and the monomer is polymerized. The kinetics of photoinitiation polymerization is very clear, the reaction is widely used in paint, ink and other fields. The polymerization mechanism of the limited solid state photopolymerization (topological polymerization) system has also been thoroughly studied. The solid state photopolymerization of thiophene with halogenated derivatives is less reported and the reaction process is less studied. It is generally believed that these reactions are initiated by free radicals by breaking the carbohalogen bond under light. In this paper, two trianiline-like dihalobis (3C4ethyldioxothiophenyl) benzomethane monomers were synthesized and polymerized under light. It was found that different substituted halogens produced different IR and UV spectra. Neutral polymers can be used as bromine and iodine sensors with a detection limit of 50 ppm, and the polymers are unstable in a high concentration of halogen solution. In addition, the polymerization kinetics shows that the polymerization order is 1 / 2 to the monomer, and the apparent reaction rate constant of the two monomers is very close to that of the two monomers under 254 nm ultraviolet light, that is, the two monomers have the same reaction rate.
【学位授予单位】：武汉大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.5

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