聚苯胺及苯胺低聚体的合成与自组装

发布时间：2017-12-26 20:15

本文关键词：聚苯胺及苯胺低聚体的合成与自组装　出处：《中国科学技术大学》2017年硕士论文　论文类型：学位论文

【摘要】：自从发现掺杂后聚乙炔的电导率可以大幅度提升以来,有关有机导电高分子的研究引起了越来越多的人的注意。聚苯胺由于其合成方法简单,单体原料容易获得,并且经掺杂后具有很好的导电性,成为导电高聚物领域的研究热点。研究表明聚苯胺分子链的聚集形态会对其导电性能产生显著的影响,因此,控制聚苯胺的形貌具有重要的意义。因为聚苯胺的溶解性差,对于形貌控制和研究带来不利影响。然而,苯胺的低聚体衍生物具有良好的溶解性,因此,本论文从苯胺低聚体衍生物入手,对其自组装行为和形貌进行探索研究,以求对聚苯胺的形貌控制提供有价值的信息。研究工作主要包括以下三个方面:1.通过4,4'-亚甲基双(异氰酸苯酯)与N-苯基对苯二胺缩合,得到有机小分子。以此有机小分子为模板合成具有一定有序性的聚苯胺。利用傅立叶红外光谱(FT-IR)、X射线衍射仪(XRD)、紫外分光光度计(UV-Vis)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等分析手段对其进行了形貌和结构的表征。利用热重分析仪(TG)、电化学工作站等分析手段,进一步比较无模板聚苯胺和模板聚苯胺热性能和电性能的不同。2.设计、合成了三种苯胺低聚物,包括双羧基封端的苯胺五聚体、3,5-二氨基苯甲酸与二苯胺缩合聚合物以及4-二苯胺基苯甲醛衍生物与对苯二胺缩合聚合物。通过核磁共振氢谱(1H-NMR)、核磁共振碳谱(13C-NMR)、傅立叶红外光谱(FT-IR)、X射线衍射仪(XRD)、紫外分光光度计(UV-Vis)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等分析手段对其结构和形貌进行表征,然后利用热重分析仪(TG)对其热性能进行分析。3.设计、合成了含有苯胺二聚体的苯乙烯衍生物,通过自组装-自由基聚合的方法,成功地制备了聚合物纳米片层材料。单体和聚合物的结构通过核磁氢谱/碳谱和红外光谱进行了分析确认,其自组装行为通过电子显微镜、X-射线衍射进行了研究。实验结果表明,二苯胺基苯乙烯单体在甲苯和丙酮的混合溶剂中可以自组装成为二维纳米片层,并能与马来酰亚胺进行自由基共聚反应,形成尺寸数微米、厚度2纳米的聚合物片层材料。本研究的结果证明,将自组装与自由基聚合结合是一种制备聚合物二维纳米片层材料的有效方法。
[Abstract]:Since the conductivity of polyacetylene (polyacetylene) can be greatly improved after doping, more and more attention has been paid to the research of organic conducting polymers. Due to its simple synthesis method, polyaniline is easy to obtain from monomers and has good conductivity after doping. It has become a research hotspot in the field of conductive polymers. The research shows that the aggregation morphology of polyaniline molecular chain has a significant influence on its electrical conductivity. Therefore, it is of great significance to control the morphology of polyaniline. Because the solubility of polyaniline is poor, it has adverse effects on morphology control and research. However, the oligomer derivatives of aniline have good solubility. Therefore, starting from the derivatives of aniline oligomers, the self-assembly behavior and morphology of aniline were explored in order to provide valuable information for the morphology control of polyaniline. The research work mainly includes the following three aspects: (1.) small organic molecules are obtained by condensation of 4,4'- methylene bis (benzyl isocyanate) and N- phenyl to benzyl two amine. The organic small molecule is used as a template to synthesize polyaniline with a certain order. The morphology and structure were characterized by Fu Liye transform infrared spectroscopy (FT-IR), X ray diffractometer (XRD), ultraviolet spectrophotometer (UV-Vis), scanning electron microscope (SEM) and transmission electron microscope (TEM). The thermogravimetric analyzer (TG) and electrochemical workstation were used to compare the thermal and electrical properties of template free polyaniline and template polyaniline. 2., three kinds of aniline oligomers were designed and synthesized, including dicarboxylic terminated aniline five polymers, 3,5- two amino benzoic acid and two aniline condensation polymers, and 4- two aniline benzaldehyde derivatives and polyaniline two amine condensation polymers. By nuclear magnetic resonance spectroscopy (1H-NMR), nuclear magnetic resonance spectra (13C-NMR), infrared spectroscopy (FT-IR), Fu Liye X - ray diffraction (XRD), ultraviolet spectrophotometer (UV-Vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM) on the structure and morphology analysis etc. then, using thermogravimetric analyzer (TG) on the thermal performance analysis. 3., a styrene derivative containing aniline two polymer was designed and synthesized. The polymer nanoscale material was successfully prepared by self-assembly radical polymerization. The structures of monomers and polymers were analyzed by NMR / C and FTIR. The self assembly behavior was confirmed by electron microscopy and X- ray diffraction. The experimental results show that the two aniline styrene monomer can be self assembled into two dimensional nanosheets in toluene and acetone mixed solvents, and can be copolymerized with maleimide for free radical polymerization, forming a size of 2 micron and polymer nanoscale material. The results of this study show that the combination of self-assembly and free radical polymerization is an effective method for the preparation of two-dimensional polymer layer materials.
【学位授予单位】：中国科学技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O633.21

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