基于多臂核壳微凝胶球水下超疏油防污涂层的构建及其多重自修复机理研究

Underwater superoleophobic and antifouling surface materials have wide applications in biomedical materials, biological, chemical and marine ships, etc. However, the existing underwater superoleophobic and antifouling surfaces cannot serve in the underwater environment for a long time due to low durability, poor antifouling property and no self-repairing capability. In this project, multi-arm core-shell microgel spheres were prepared by emulsifier-free emulsion polymerization and surface grafting modification of multiple hydrogen-bonding antifouling block copolymers, and then self-repairing underwater superoleophobic and antifouling surfaces were constructed via the blending of resins and microgels or the self-assembly of microgel spheres. These microgel spheres can have swelling abilities and antifouling property via adjusting the ratio of core and shell components and the grafting density of antifouling block copolymers on microgel spheres, and thus the underwater superoleophobicity and antifouling property of surface can be achieved. In the meantime, this coating can possess the self-repairing capability in the surface and the interior with combining the salt-responsive migration of the hydrophilic segments and dynamic reversible assembly of multiple hydrogen bondings. The relevance of the hierarchical structure, chemical composition and oleophobic antifouling property and the repairing behavior of the surface and interior in the coating will be studied in detail in order to explore the key factors for the preparation of self-repairing under superoleophobic and antifouling surfaces and their multiple self-repairing mechanism. This study will provide the theoretical basis for developing the long-term oleophobic or antifouling surfaces.

水下超疏油防污表面材料在生物医用材料、生物化工及海洋船舶等领域具有广阔的应用前景，但是现有疏油或防污表面存在耐用性差、耐污性差和无自愈合性等缺陷，无法在水下环境中长期使用。本项目以无皂乳液聚合和多重氢键抑污嵌段共聚物表面接枝制备多臂核壳微凝胶球，并通过其与树脂共混、组装构建自修复水下超疏油防污涂层。通过调控微凝胶球的核壳比、嵌段共聚物的接枝密度，赋予微凝胶球溶胀性和抑污性，获得表面水下超疏油和防污性能，同时结合微球表面亲水链段盐响应迁移和多重氢键作用，赋予涂层表面结构、化学组成和本体自修复功能；探讨自修复涂层表面的粗糙结构、化学组成与疏油防污性能的关联性以及涂层表面和本体在人工损伤后修复行为，揭示自修复型水下超疏油防污涂层构建的关键控制因素及多重自修复机制，为发展长效高性能疏油、抗生物黏附等防污表面提供科学依据。

现有疏油、疏水或防污等特殊润湿性表面材料存在耐用性差、耐污性差和无自愈合性等缺陷，无法长时间服役。本项目紧紧围绕国家需求和课题任务书要求，开展了大量基于功能微球的自修复特殊润湿性表面材料的研究，项目已按照预期研究计划执行，已经完成的主要研究内容有：已通过ATRP、接枝等方法合成了系列含多重氢键基元和抑污链段的低聚物，并优化了聚合工艺条件，并将低聚物接枝到微凝胶球表面，通过调节微凝胶球的核壳比，调控了其溶胀性和机械强度。同时还合成了pH响应嵌段共聚物，并对聚苯乙烯微球的自组装形成的反蛋白石结构表面进行了改性研究，制得了润湿性可逆转变的表面。通过改性聚倍半硅氧烷和pH响应单体的引入合成了pH响应型光固化聚氨酯树脂，并应用于油水分离润湿性表面材料。通过合成的含多重氢键聚氨酯，并基于微球的自组装构筑了规整结构涂层，研究了其水下超疏油和防生物黏附性能及其协同效应，获得了水下超疏油防污表面的全面精准构效关系。所构建的涂层表面水下油接触角大于150o，且对牛血清白蛋白等模拟污染物有抑制作用，具有海洋防污效果。研究了微球溶胀及抑污链段的响应迁移等因素对表面自修复行为的控制机制；研究了聚氨酯中多重氢键基元含量对涂层本体自修复的影响过程，提出了微球亲水溶胀、抑污链段的亲水迁移和多重氢键基元动态可逆组装等作用是涂层自修复的关键控制因素。此外，通过合成聚氨酯树脂和改性石墨烯、功能纳米粒子的复合制备了双重自修复导电超疏水多功能涂层，研究了导电、超疏水等性能与涂层表面结构的关联性，研究了有机相与无机相间弱相互作用力对涂层本体自修复过程的影响。本项目深入揭示了特殊润湿表面材料制备及其服役性能的关键控制因素，为自修复型表面材料构建提供了理论支撑和实验依据，对特殊润湿性表面材料的仿生设计具有重要的指导意义。基于上述研究成果发表相关SCI论文9篇；申请国家发明专利5项，授权4项；培养博士生1名，硕士生2名。