【作者】 李敏；

【导师】 程林；

【作者基本信息】 东南大学 ， 化学， 2019， 硕士

【摘要】 近年来,随着建筑、电子、军事以及航空航天等领域的不断进步,传统的材料已经不能满足发展的要求,因而智能高分子材料应运而生。相比于其他智能材料,智能高分子材料具备易于合成加工,分子设计性强,密度小以及制备成本低廉等优点。在智能高分子材料的实际应用中,自修复是其必不可少的一项重要功能。自修复高分子材料可以通过加热、光照等方式对内部缺陷进行修复,从而达到增强材料的强度和延长使用寿命的效果,因而广泛应用于建筑、通讯、交通、国防、医疗和日用品等领域。另外,智能高分子材料的刺激响应功能也是一个重要组成部分,可以分为热响应、光响应以及化学刺激响应等。本论文将金属-硫醚可逆配位相互作用与热塑性高分子相结合,制备出具有自修复功能和刺激响应功能的智能高分子材料。首先,本论文通过对聚合物的结构参数进行设计并采用可逆加成-断裂链转移聚合（RAFT）制备出一系列具有不同分子量的硫醚基二嵌段聚合物,然后将其与贵金属银双（三氟甲磺酰胺）（Ag（NTf₂））结合,制备出聚（甲基丙烯酸甲酯）-b-聚（丙烯酸甲基硫代乙酯-co-丙烯酸丁酯）-银（PMMA-b-P（BA-co-MTEA）-Ag）杂化聚合物。这种银-硫醚可逆配位杂化聚合物内部存在着两种交联方式:（1）嵌段聚合物中存在微相分离,玻璃态PMMA域充当聚合物连续体的物理交联剂;（2）聚合物中银-硫醚配位相互作用充当化学交联剂,使聚合物形成交联网络结构。这种杂化聚合物具有优异的机械性能,断裂伸长率可以达到1000%,断裂强度可以达到1-5 MPa。同时,该杂化聚合物具备较好的自修复能力,恢复率可以达到80%。另外,该杂化聚合物具备热塑性材料的热加工性能,可以通过热加工的方式制备成所需要的形状。其次,本论文在银-硫醚可逆配位杂化聚合物的基础上进行深入研究,制备出价格更加低廉、功能更加多样的铜（I）-硫醚可逆配位杂化聚合物,聚（甲基丙烯酸甲酯）-b-聚（丙烯酸甲基硫代乙酯-co-丙烯酸丁酯）-溴化亚铜（PMMA-b-P（BA-co-MTEA）-CuBr）。该杂化聚合物依然是双交联结构,因而具备优异的机械性能,断裂伸长率最高可达700%,断裂强度最高可达7.5 MPa。同时,聚合物具备良好的自修复性能（恢复率可达30%）和热加工性能。值得注意的是,铜（I）-硫醚杂化聚合物薄膜可以对HCl蒸汽和过氧化氢溶液的刺激快速做出响应,并以颜色变化的方式显示出来,因而可以作为柔性膜传感器以及一次性氧化剂测试塑料在工业领域广泛应用。更多还原

【Abstract】 Recently,in order to meet the needs of the development of technology,to prepare the smart materials which used in construction,electronics,military,and aerospace fields have attached more and more attention.Compared with the other materials,smart polymer materials have great advantages,such as simple preparation,strong molecular design,low density and inexpensive.Self-healing was an important function of smart polymer materials in the practical application,and the Self-healing polymers could achieve repair by heating or illumination to enhance the strength and prolong service life of materials.Therefore,self-healing polymers have been widely used in the fields of construction,communications,transportation,national defense,medical and daily necessities.In addition,the stimuli-responsive function of smart polymer which can be responsive to thermal,light and chemical,is also an important component.In this paper,a series of smart polymer materials with self-repairing function and stimuli response function was prepared by combining metal-thioether reversible coordination interactions with thermoplastic polymers.Firstly,a series of thioether-based diblock polymers with different molecular weights were prepared by Reversible Addition-Fragmentation Chain Transfer polymerization（RAFT）,and then combining with noble metal Silver bis（trifluoromethanesulfonamide）（Ag（NTf₂））to prepare poly（methyl methacrylate）-b-Poly（methyl thioethyl acrylate-co-butyl acrylate）-silver（PMMA-b-P（BA-co-MTEA）-Ag）hybrid polymers.Two ways of crosslinking inside the polymer are involved:（1）There is microphase separation in the block polymer,and the glassy PMMA domain acts as a physical crosslinker for the polymer continuum;（2）The silver-thioether coordination interaction in polymers acts as a chemical crosslinker causing polymers to form crosslinked network structures.The Ag-thioether Reversible coordination hybrid polymers have excellent mechanical properties,the strain at break can reach 1000%,and the stress at break can reach 1-5 MPa.Meanwhile,the polymers exhibit good self-healing ability and the recovery rate can reach 80%.In addition,the polymers have the thermal processing properties of thermoplastic materials and can be prepared into desired shapes by thermal processing.Secondly,based on the study of Ag-thioether reversible coordination hybrid polymers,the cheaper and more versatile copper（I）-thioether reversible coordination hybrid block polymers（poly（methyl methacrylate）-b-Poly（methyl thioethyl acrylate-co-butyl acrylate）-silver（PMMA-b-P（BA-co-MTEA）-Ag））with dual-crosslinked structure were prepared.Those polymers exhibite excellent mechanical properties,and the strain at break can be up to 700%,and the breaking strength can be up to 7.5 MPa.At the same time,the polymers also have excellent self-healing properties（recovery rate up to 30%）and thermal processing properties.Notably,the films of copper（I）–thioether block polymers exhibited very fast responses toward hydrochloric acid vapor and hydrogen peroxide solution by color changing.The irreversible sensory properties of these hybrid materials make them suitable for applications in industries as flexible membrane sensors and disposable oxidant testing plastics.更多还原