双智能响应性石墨烯复合物的制备、表征及其应用探究

发布时间：2018-03-23 15:34

本文选题：还原氧化石墨烯　切入点：智能高分子材料　出处：《辽宁大学》2017年硕士论文

【摘要】：智能响应性石墨烯由于兼具智能高分子的智能响应特性以及石墨烯优良的物理性能而受到了广泛关注。智能响应性石墨烯纳米复合材料的制备包括两种常用的制备方法,即“共价法”和“非共价法”。与共价修饰法相比较,非共价修饰法具有对石墨烯共轭结构、机械和电学性能影响小的优点,因而能够很好的保持石墨烯原有的物理性质。然而,对于那些没有共轭结构的智能高分子来言,这种修饰方法则要求在智能高分子结构中植入具有大π键结构的“连接”部位,从而使其能够通过非共价作用有效的修饰在石墨烯表面。聚合离子液体是通过不饱和的离子液体单体聚合而获得的聚合物。由于聚合离子液体含有大π键结构,已被证明可以通过非共价作用有效的修饰在碳基纳米材料表面。此外,这种聚合物还具有独特的离子交换性,可利用这种性质通过控制阴离子的种类,赋予聚合物智能响应性,使其实现亲疏水性的转换。更为重要的是,还可以通过离子交换作用向复合材料中引入具有功能性的阴离子,从而实现功能性材料的构建。因此,如果将聚合离子液体作为“连接”部位引入,不仅可以实现无共轭结构的智能高分子材料在石墨烯上表面的非共价修饰,而且还可以赋予复合物以多重智能响应性和功能性。基于以上的分析,本论文主要开展了以下两部分工作:1.本文首先建立了一种具有普适性的智能石墨烯的合成方法,即首先利用原位聚合,通过自由基引发的方法合成了聚合物poly(NIPAm-co-ViEt ImBr),然后利用聚合物中聚合离子液体所含的大π键结构,通过非共价修饰作用进一步合成了水溶性较好的智能性的石墨烯纳米复合材料poly(NIPAm-co-ViEt Im Br)-rGO。实验过程中运用TEM,AFM,UV-vis,XPS和FT-IR等方法对合成的复合物的形貌和结构进行了一系列的表征。并进一步通过宏观观察及利用UV-vis表征对复合物的温敏性和离子性进行了监控测试,实验结果表明,合成的复合物poly(NIPAm-co-Vi Et ImBr)-rGO具有良好的双重智能响应性,并且循环可逆,具有良好的开关效应。此外,实验还利用复合物中聚合离子液体独特的离子交换性制备了两种功能性材料,并进行了进一步的表征和应用探究。2.本文为进一步考察合成方法的普适性,利用相同的方法合成了具有pH响应性的复合物poly(AA-co-ViEt Im Br)-rGO。实验对复合物进行了TEM,TGA,UV-vis,XPS和FT-IR等方法的表征,证明了已成功合成复合物poly(AA-co-ViEtImBr)-rGO,并对复合物的双重智能响应性进行了监控测试,实验结果表明复合物具有pH响应性和温度响应性,且循环可逆,具有良好的开关效应。
[Abstract]:Intelligent responsive graphene has attracted much attention because of its intelligent response characteristics of intelligent polymers and excellent physical properties of graphene. The preparation of intelligent responsive graphene nanocomposites includes two common preparation methods. That is, "covalent method" and "non-covalent method". Compared with covalent modification method, noncovalent modification method has the advantages of little influence on the conjugate structure, mechanical and electrical properties of graphene, so it can keep the original physical properties of graphene well. For intelligent polymers without conjugate structures, this modification requires the insertion of "join" sites with large 蟺 bond structures in smart polymer structures. So that it can be effectively modified on the surface of graphene by non-covalent action. Polymeric ionic liquids are obtained by polymerization of unsaturated ionic liquid monomers. Because polymeric ionic liquids contain large 蟺 bond structures, It has been proved that the polymer can be effectively modified on the surface of carbon based nanomaterials by non-covalent action. In addition, the polymer has unique ion exchange property, which can be used to give the polymer intelligent responsiveness by controlling the type of anions. More importantly, functional anions can also be introduced into the composite materials through ion exchange, so that functional materials can be constructed. If the polymeric ionic liquid is introduced as the "joint" site, the noncovalent modification of intelligent polymer materials with no conjugated structure on the surface of graphene can be realized. Based on the above analysis, this paper mainly carried out the following two parts of work: 1.In this paper, a universal synthesis method of intelligent graphene is established. That is to say, in situ polymerization, the polymer poly(NIPAm-co-ViEt imbrine was synthesized by the method of free radical initiation, and then the large 蟺 bond structure of polymerized ionic liquid was used. Poly(NIPAm-co-ViEt Im Br-rGO, a water-soluble and intelligent graphene nanocomposite material, was further synthesized by non-covalent modification. The morphology and structure of the synthesized composites were characterized by TEM AFM UV vis XPS and FT-IR during the experiment. Furthermore, the temperature sensitivity and ionic properties of the complexes were monitored and tested by macroscopical observation and UV-vis characterization. The experimental results show that the synthesized poly(NIPAm-co-Vi et ImBr)-rGO has good dual intelligent response, cyclic reversible and good switching effect. In addition, two kinds of functional materials were prepared by using the unique ionic exchangeability of polymeric ionic liquids in the complex, and further characterization and application were carried out. 2. In order to further investigate the universality of the synthesis methods, The pH responsive complex poly(AA-co-ViEt Im Br-rGO was synthesized by using the same method. The complex was characterized by TEMGA-TGA UV-vis-XPS and FT-IR methods. It was proved that the complex poly (AA-co-ViEtImBr-rGOA) was successfully synthesized, and the dual intelligent response of the complex was monitored and tested. The experimental results show that the complex has pH and temperature response, and the cycle is reversible and has a good switching effect.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ127.11;TB33

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