【作者】 肖雪清；

【导师】 林金火；

【作者基本信息】 福建师范大学 ， 高分子化学与物理， 2014， 博士

【摘要】 共轭聚合物具有独特的光电性能,广泛用作导电聚合物、有机发光二极管、太阳能电池和场效应晶体管等。而用作有机电子器件时,其性能与共轭聚合物的化学结构、纯度及其形貌有关。例如,利用自组装技术,共轭聚合物的光学物理性能可以通过调节微纳米颗粒的几何形状进行优化设计与调控。然而,具有明确形貌的共轭聚合物微纳米颗粒的制备过程难以控制,因此,开发一种快速、便捷的制备多形貌的共轭聚合物微纳米颗粒的方法具有重要的意义。本论文以固相氧化偶联法合成的聚烷基芴、聚萘、聚烷基萘醚、芴-萘丁醚共聚物和聚烷基吲哚等一系列聚合物为研究对象；通过不良溶剂自组装制备具有不同形貌的芳香类共轭聚合物微纳米颗粒,解决共轭聚合物难制备成球状颗粒的问题,实现共轭聚合物微纳米颗粒形貌可控。重点考察各种不良溶剂氛围中,芳香类共轭聚合物自组装的有效条件及其形貌的控制。研究发现,利用不良溶剂自组装,实现了芳香类共轭聚合物微纳米颗粒形貌有效调控；其自组装过程是“沉淀-溶解”过程。共轭聚合物结构是自组装形貌的决定性因素。共轭聚合物分子链中的长烷基侧链,会破坏其有序度,降低其结晶度,这有利于微纳米球的形成,聚9,9-二己基芴、聚烷氧基萘便可自组装成微纳米球；若共轭聚合物分子链中的烷基侧链变短,聚合物结晶度提高,较容易形成片状结构,聚萘就只能自组装得到表面包裹纳米片的球状结构；二元共聚物体系的有序度与共聚组分比例有关,可实现纳米片、类球体、球等多种形貌可控自组装。其次,自组装条件是共轭聚合物自组装的另一决定性因素,改变自组装有效条件,可实现共轭聚合物形貌可控自组装。以聚(9,9-二己基芴)为自组装体系,便可制得球、半球、多孔膜、蝴蝶结、纳米线等多种形貌；其次,微纳米球的粒径和分布可通过聚合物浓度、进样量和良溶剂极性进行调控。具有蝴蝶结、类球体和片状结构的微纳米颗粒具有超疏水性能,最大接触角为153.7°。且与块状聚合物相比,微纳米球、多孔膜、半球、蝴蝶结结构的聚9,9-二己基芴微纳米颗粒的荧光发射光谱发生红移；微纳米球的红移最大。此外,用固相研磨法制备烷基吲哚聚合物微纳米颗粒,具有较好的耐热性能和光学性能。可见,不良溶剂自组装氛围法是一种快速、简便制备微纳米结构可控的有效方法。更多还原

【Abstract】 Because of the unique photoelectric properties, conjugated polymers have been widely applied in the conductivity polymer, field-effect transistors, light emitting diodes, and so on. In addition, the property of the organic devices was related to the chemical structure, purity, and the morphology of the conjugated polymer.The performances of the conjugated polymer could be controlled and optimized through the fabrication of miceo-and nanostructural shapes such as micro-and nanoparticles, nanofibers, and so on. However, preparing well-defined micro-and nanostructural particle is not easy, because the formation processes are hard to control. Therefore, developing a simple, rapid, and efficient approach to fabricate micro-and nanostructures of conjugated polymers with controllable morphology and size is of high importance.In this work, the conjugated polymers of poly (9,9-dialkylfluorene), poylynaphthalene, poyly(naphthalene alkylether), fluorene-co-naphthalene butyl ether polymer and the poly(alkyl indole) were synthesized by the solvent free solid oxidant coupling polymerization. Meanwhile, the micro-and nanostructures of the polymer with different geometries were formed by the non-solvent vapor method and the different morphology of the polymer could be controllable by self-assembly. The main work focused on optimizing the self-assembling conditions and forming micro-and nanostructures of the polymer with controllable morphology.It was found that the morphology of micro-and nanostructures of the conjugated polymes could be completely prepared by self-assembly of the nonsolvent vapor method,, which was a process of slow-solution-precipitation. The structure of the conjugated polymers was a dominant factor to obtain the micro-and nanostructure with controllable molophology. When the conjugated polymers had a long length alkyl chain in the main chain, the regularity of the polymers would reduce, and then their crystallinity was low. The micro-and nanostructural spheres were easily formed by the polymers with low crystallinity. So, micro-and nanostructural spheres of the poly (9,9-dihexylfluorene) and the poyly(naphthalene alkylether) were fabricated by the nonsolvent vapor methods. On the contrary, the conjugated polymers with a short alkyl chain would have high crystallinity, and the micro-and nanosheet would be formed by the self-assembly. For example, the micro-and nanospheres with sheet of the poylynaphthalene were fabricated in the nonsolven vapor. Furthermore, the geometrical shapes of the micro-and nanostructure of copolymers, such as nanosheets, big-leaf hydrangea structures, and spheses, could be controlled by the adjustion of the ratio of monomers. On the other hand, the parameters of the self-assembly was another important factors. The controllable morphology of the conjugated polymers could be achieved by optimization condition. The porous, nanowire, hemisphere, sphere and butterfly-like structures of the poly (9,9-dialkylfluorene) were formed by turning the conditions of self-assembly. Finally, the size and the distribution of the micro-and nanospheres could be controlled by the concentration of the polymers, volume of the polymers and the polar of the good solvent.The butterfly-like structures, big-leaf hydrangea structures, and the spheres with nanosheets were superhydrophobic, and the bigest contact angle was153.7°. Compared with bulk conjugated polymers, the fluorescence emission wavelength of micro-and nanostructures of conjugated polymers, such as spheres, porous, hemispheres, and butterfly-like structures, had shifted to red. In addition, the nanoparticle of the poly (alkyl indole), which was prepared by solvent free solid oxidant coupling polymerization, had good thermostability and optical property. Therefore, the nonsolvent vapor method was a simple, rapid, and efficient approach to fabricate the diferent morphology of the polymers.更多还原