【作者】 姚雷；

【导师】 王策； 刘新才；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2011， 博士

【摘要】 聚苯胺是一种性能较好的导电高分子材料,但由于其难以加工的特点限制了在实际当中的应用,因此人们对其在应用领域的研究逐渐转到其齐聚物上来,为克服苯胺齐聚物机械强度差、稳定性不好等缺点,人们通过分子设计将苯胺齐聚物与其他材料复合,合成具有电活性的新型材料。在此基础上,本论文从分子设计出发,合成了四种含有苯胺齐聚物链段的电活性单体,然后利用亲核取代反应与氧化偶联聚合等方法合成一系列分子链段中含有苯胺链段的电活性特种工程塑料聚合物。利用一步亲核取代方法,合成了含有母体苯胺四聚体大测基的双氟单体,通过三元共聚的方法合成侧链含苯胺四聚体链段的电活性聚芳醚酮聚合物,该聚合物具有较好的溶解性和热稳定性。对原有的合成方法进行改进,重新设计合成路径,利用亲核取代与氧化偶联的方法合成了主链含苯基封端苯胺四聚体的氟酮大单体,通过三元共聚的方法合成了两种溶解性好的主链型电活性聚芳醚酮聚合物,通过对其性能的研究总结了不同基团含量对材料的性能的影响及其变化规律。设计合成一种主链含苯基封端苯胺四聚体和腈基的双氟单体,通过亲核取代合成一种电活性聚芳醚腈聚合物,其具有极好的溶解性和介电性能、较好的热稳定性与机械性能,最终得到的聚合物具有广阔的应用前景。分别利用亲核取代反应与氧化偶联两种聚合路线合成含苯基封端苯胺四聚体的电活性超支化聚合物,对比研究两种合成方法对聚合物材料性能的影响。更多还原

【Abstract】 Due to the special and interesting properties of conjugated polymers (e.g. polyacetylene, polythiophene, polyaniline, etc.), they can be widely applied in lightweight batteries, electrochromic display devices, light-emitting diodes, optical switches, etc. However, as conventional polymers, these conjugated polymers have defects in the molecular weight distribution, conjugated length and structure. The properties of the conjugated polymers are therefore the statistic averages of each structure. This renders the difficulty of controlling the properties of materials through tailoring of their molecular structure. In comparison, monodispersed conjugated oligomers, which have step-by-step increasing size of theπ-system, can establish detailed structure-property relationship for corresponding polymers. On the other hand, monodispersed conjugated oligomers themselves are a kind of conductive materials. In order to spread its application, recent years, people do a lot of research to compose the oligomer with other special materials. Considering the above points, the investigations on producing new special materials containing conductive oligomer provide the foundation for the development of the application of conductive polymers.In this paper, we synthesized a series of monomers containing oligoaniline. By using them, we synthesized a series of polymers which contained oligoaniline in the main or side chain. The preparative processes are recorded as below: 1. Synthesis and characterization of a side-chain electroactive poly (aryl ether ketone)We synthesized a monomer containing parent aniline tetramer in the side chain through nucleophilic substitution. By using it, we synthesized a new electroactive poly (aryl ether ketone) containing electroactive segment in the side chain. We found that it had good thermal stability and electrical properties.2. Synthesis and characterization of soluble electroactive poly (aryl ether ketone) containing oligoaniline in the main chainWe synthesized a monomer containing phenyl-capped aniline tetramer in the main chain via nucleophilic substitution and oxidative coupling. By using it, we synthesized two soluble electroactive poly (aryl ether ketone) containing oligoaniline in the main chain. The introduction of nitrile groups and sulfonate groups improved the solubility. Furthermore, we found that the nitrile groups improved the solubility and dielectric properties of the electroactive poly (aryl ether ketone). The sulfonate groups strengthened the intermolecular force between polymer segments and therefore enhanced the thermal stability.3. Synthesis and characterization of electroactive poly (aryl ether ether nitrile) containing oligoaniline in the main chainWe synthesized a monomer containing phenyl-capped oligoaniline and nitrile groups in the main chain. Comparing to the monomer containing phenyl-capped oligoaniline in the main chain we synthesized earlier, it has excellent solubility and the synthetic process was much easier. By using this monomer, we synthesized a new electroactive poly (aryl ether ether nitrile). This new polymer has excellent processing performance and could be taken into actually use in the future.4. Synthesis and characterization of electroactive hyperbranched poly (aryl ether ketone) and poly (aryl ether ether nitrile)We synthesized two different electroactive hyperbranched polymers using two different methods. By way of oxidative coupling, we synthesized the electroactive hyperbranched poly (aryl ether ketone). By using nucleophilic substitution, we synthesized the hyperbranched poly (aryl ether ether nitrile). Comparing the properties of the two polymer we synthesized, the advantages and shortages of the different synthetic processes would be understood.更多还原