The Synthesis And The Self-assembly Of The Aromatic Conjugated Polymers

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.