具有缓蚀和自修复双重功能微球材料的构筑及其性能研究

The construction of a long-term smart metal protection system has important scientific significance and great national economic value. Therefore, this project intends to design and prepare three kinds of microspheres, in which corrosion inhibitor and self-healing agent are loaded in the different phases of the same body. After each of the three kinds of microspheres is mixed in a water-borne polyurethane, the obtained composite coating will perform dual functions of active anti-corrosion and self-healing. The preparation of the first,raspberry-like, microspheres starts from inhibitor-loaded and pH-responsive hollow meso-porous SiO2 (m-SiO2) particles, fabricated through micro-emulsion and radiation-induced grafting technique. The m-SiO2 particles are used to construct Pickering emulsion and mini-emulsion system respectively, from which, raspberry-like microspheres loading inhibitor and self-healing agent in individual phases will be obtained through interface polymerization and radiation-induced emulsion polymerization. The release of the inhibitor and self-healing agent can be controlled by using the UV-degradable monomer or the addition of the near infrared (NIR) photothermal responsive polypyrrole (PPy) nanoparticles. The second, snowman-like microspheres with the inhibitor and self-healing agent loaded in each bulb are prepared by the combination of seed emulsion polymerization and dynamic swelling-dissolving process. The third, core-shell structured intrinsic self-healing microspheres are designed by radiation-induced grafting of polymer chains with photo-reversible moieties (5-acetylaminopentyl acrylate) on inhibitor-loaded rigid polymer cores, which can self-reinforce the bulk material composed by the microspheres. The research work on the validation of the integration of self-healing coating and active anti-corrosion in this project will provide new theories and methods on the preparation of efficient metal protection materials. The research results will certainly have significant application value.

构筑长效智能型金属防腐体系，具有重要科学意义和重大经济价值。本申请项目拟设计制备三种同体不同位负载缓蚀剂和自修复剂的微球，与涂料复合，发挥缓蚀剂主动防腐和涂层自修复双重功能。采用微乳液和辐射接枝的方法制备具有pH响应性、负载缓蚀剂的中空介孔二氧化硅微球，用此微球分别构筑 Pickering乳液和细乳液体系，结合界面和辐射乳液聚合，得到不同部位分别负载缓蚀剂与自修复剂的树莓型微球，借助于可光降解官能团的单体或添加聚吡咯等纳米粒子，自修复剂可UV或 NIR光响应释放；通过种子聚合与溶胀-溶解法，制备缓蚀剂与自修复剂各负载一端的雪人型微球；利用辐射接枝法，在包覆缓蚀剂的刚性聚合物微球上接枝"本征型"自修复聚合物链，获得自增强本征型自修复缓蚀微球材料。通过对涂层自修复和主动防腐功能集于一体的概念验证研究，必将为高效金属防腐涂层材料的制备建立新理论和新方法，研究成果具有重要的应用价值。

金属防腐是世界性难题，构筑长效智能型金属防腐体系是涂层防腐技术的关键。本项目按计划从防腐微球的设计与构筑出发，制备了三种同体不同位负载缓蚀剂和自修复剂的微球，探讨了SiO2中空介孔微球及其与高分子笼空微球复合的机理，研究了防腐微球和水性聚氨酯复合形成的防腐涂层的防腐和自修复性能，提出了构筑具有特殊形貌防腐微球的新方法。经过四年的探索，本项目取得了以下主要成果：①利用乳液聚合和辐射接枝技术制备出负载缓蚀剂的刺激响应性中空介孔SiO2微球。实验证明介孔SiO2壳层形貌与聚苯乙烯模板微球表面电荷性质密切相关，中空微球所负载的防腐剂的释放具有显著的环境响应性；②合成了含呋喃的聚氨酯单体，并进一步与双马来酰亚胺小分子反应，得到了基于热可逆Diels-Alder反应的新型自修复剂；③以中空SiO2微球为种子微球，通过种子分散聚合与溶胀-渗透致孔法相结合，成功制备了新颖的雪人型中空SiO2/多孔PS复合微球；④利用辐射接枝技术成功制备了具有较高力学强度、表面接枝自修复功能高分子链，内部负载缓蚀剂的本征型自修复多孔聚苯乙烯微球。在成功制备上述特殊结构防腐微球和自修复剂的基础上，将其与环境友好的水性聚氨酯乳液复合，构筑了新型防腐涂层体系，验证了这种新颖的防腐体系对金属具有防腐和自修复双重功能。.以上研究成果及相关工作已在Applied Surface Science、Particle &.Particle Systems Characterization、Electrochimica Acta、ACS Applied Materials & Interfaces 和Journal of Materials Chemistry A等SCI或CSCD检索期刊上发表论文共30篇；获授权专利5项；还有数篇论文正在投稿过程中。本项目研究工作已达到预期的研究目标，成功制备出具有智能响应性和可负载性的中空二氧化硅微球以及同时具有环境响应性和自修复性能的笼空状复合微球，并对制得的微球的环境响应性能、防腐性能以及自修复性能进行了研究，制备的微球均表现出理想的环境智能响应性和金属防腐蚀性能，为长效金属防腐涂层材料的制备建立了新理论和新方法，研究成果具有重要的实际应用价值。