【作者】 丁世海；

【导师】 张万金；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2009， 博士

【摘要】 导电聚合物的出现不仅打破了高分子仅为绝缘体的传统观念,而且它的发现和发展为低维固体电子学,乃至分子电子学的建立和完善做出重要的贡献,成为材料科学的研究热点。同时,导电高分子具有特殊的结构和优异的物理化学性能使它在能源、信息、光电子器件,以及电磁屏蔽、金属防腐和隐身技术上有着广泛的应用前景。由于纳米材料拥有小尺寸效应,大比表面积等特性,所以导电高分子的纳米复合材料被认为是最有希望得到广泛应用。本论文是采用自组装法和界面聚合法制备了一系列多种形貌的纳米复合材料,并且对复合材料的性质进行了表征,主要包括四方面的工作,分别为采用成熟的界面聚合的方法制备聚苯胺纳米棒材料;通过自组装技术制备苯胺-邻氨基苯甲酸共聚物与超顺磁性四氧化三铁纳米粒子的复合材料;通过自组装技术得到聚邻甲基苯胺与多壁碳纳米管的纳米复合纤维;深入地研究了新型聚酰胺与传统聚苯胺的电化学性质。更多还原

【Abstract】 Conducting polymers have been studied extensively because of their potential applications in sensors, electrochromic devices, and electrochemical supercapacitors as well as active electrode materials. Polyaniline and its derivatives have been considered as promising materials in various applications due to their versatile properties, for example, good environmental stability, ease of processability, high conductivity, swift change in color with applied potential and a simple, and reversible acid/base doping/dedoping properties. Nanomaterials are now one of the hot points in chemistry field in recently years. With the widen and deepen of the research, the scientists are re-examing the traditional polymers with the hope to find novel properties and functions.In recent years, there has been increased interest in nanostructures of the conducting polymers, such as nanospheres, nanotubes, nanowires, and nanoparticles, mainly because they will have the advantages of both low-dimensional system and organic conductors. In addition, the multifunctionalized PANI nanostructures have also been synthesized by blending with inorganic electrical, optical, and magnetic nanoparticles to form composite nanostructures. In this paper, novel nanostructures of polyaniline were synthesized via self-assembly method. At the same, our research expanded to the nanocomposite of polyaniline and nanoparticles or carbon nanotubes with unique electric activities. Nanorods of DBSA-PANI were synthesized through an interfacial polymerization method. Controllable diameters of DBSA-PANI nanorods from 40 nm to 1μm could be obtained by tuning the molar ratio of aniline to APS. It was also found that the morphology, size of the nanostructures also depended on the concentration of DBSA aqueous solution as well as the reaction temperature. Lower concentration of DBSA and lower temperature will be helpful to the formation of rod-like nanostructures with a relative small diameter. UV-Vis and FTIR measurements confirmed that the main chain structure of these PANI products were identical to the emeraldine salt form of PANI. And a possible mechanism of the formation of the rod-like DBSA-PANI was proposed. In summary, DBSA-PANI nanorod materials could be synthesized well by a controllable interfacial polymerization with the proper conditions.A novel and simple method was used to prepare well-dispersed Fe3O4-poly (aniline-co-o- anthranilic acid) nanoparticles. The structure and morphology of the composite was characterized by FTIR, XRD and TEM, which indicated that the Fe3O4-poly (aniline-co- o-anthranilic acid) nanoparticles were about 20 nm and well-dispersed. Furthermore, it was proved that the obtained composite possesses the superparamagnetic behavior and excellent thermal stability.We have described the synthesis of POT/c-MWNT composites with improved electrical conductivity. The electrical conductivities at room temperature of 10 wt.% c-MWNTs containing POT/c-MWNTcomposite are about 20 times higher than that of POT without c-MWNTs. The morphology of POT/MWNT composites contains both the thinner fibrous phase and the larger block phase. It is presumed that c-MWNTs were used as a core in the formation of tubular shells of the fibrous POT/c-MWNT composites. FT-IR, XRD, UV–vis spectra are used to characterize the structure of POT/c-MWNT composites.The electrochemical properties of polyaniline and synthesized polyamide were investigated and discussed. In summary, from the analysis of the experimental data obtained from CV, EIS and theoretical calculations, conclusions could be drawn as following: (i) the appearance of three pairs of redox peaks in CV measurement of polyamide indicate a relatively more complicated redox process compared with conventional polyaniline. Moreover, through electrochemical calculation and analysis, an electric charge-transfer controlled process during redox of polyamide film on the surface of glassy-carbon electrode can be confirmed. (ii) Impedance spectra of synthesized polyamide and conventional polyaniline depict typical model of polymer film-coated metals in the asymmetric metal/film/electrolyte configuration. The difference in diameters of the semi-circle impedance arc indicates that polyamide film exhibits higher electronic conductivity and lower resistance than those of the conventional polyaniline. (iii) Through analysis of theoretical calculations, influences of molecular structures on the impedance of the polymers were discussed including system energy, skeleton conjugation and the Fermi energy of the bipolaron model. All the theoretical analysis further provides convincing evidences to the impedance results.更多还原