仿生自清洁梯度海洋防污涂层的制备及其界面行为机理

Aiming at the shortcomings of environmentally friendly organosilicon marine antifouling coatings, which have poor bonding strength with the base metal, and can not effectively prevent the biofouling in static water. Innovative ideas have been put forward as follows: 1) The firm combination between the coatings and the base metal is achieved by the graded distribution of film-forming resin in the preparation of the coatings vis the mechanism of polymer blending and phase separation. 2) Non-reactive silicone oil leached from the coating surface is used for simulating the mucous secretion condition of fish skin to realize the antifouling in static water, which can be defined as the bionic self-cleaning antifouling mechanism. The effective blending of polar acrylic resin and non-polar organosilicon resin will be made by synthesizing acrylic monomer modified organosilicon resin as the intermediate bonding resin. By realizing the interpenetrating network combination of modified organosilicon resin and non-polar organosilicon resin as well as the partial blending of modified organosilicon resin and acrylic resin during the coatings curing process, the prepared coatings can realize the distribution of silicone elastomer layer, modified silicone intermediate layer, and acrylic acid sealing layer from top to bottom, while non-reactive silicone oil will also be stored through gradient distribution. By analyzing the structure and properties of the coatings and the migration and leaching behavior of silicone oil, the accurate oil directional migration model and the reasonable migration interface behavior mechanism will be established. It can lay a scientific foundation for the research of bionic self-cleaning gradient antifouling marine coatings with high antifouling efficiency.

针对环境友好型有机硅类海洋防污涂料与基材的结合力差，且无法有效地防治静水环境中生物污损的缺点。提出利用多相聚合物共混及相分离机理确保制备涂层中成膜树脂的梯度分布从而实现涂层与基材的牢固结合，并利用惰性硅油从涂层表面析出来模拟鱼类皮肤表面粘液分泌实现粘附污损生物静水防除的仿生自清洁防污机制的创新思想。通过合成丙烯酸单体改性有机硅树脂作为中间连接树脂实现极性丙烯酸树脂和非极性有机硅树脂的有效共混，在涂层固化过程中借助改性有机硅树脂与非极性有机硅树脂的互穿网络结合、与丙烯酸树脂的部分共混，制备的涂层从上至下实现有机硅弹性体层，改性有机硅中间层，丙烯酸密封层的剃度分布以及惰性硅油贮存的剃度分布。通过对制备涂层的结构和性能、惰性硅油迁移析出的界面行为机理等内容的研究，建立准确的硅油定向迁移析出模型和合理的迁移析出行为机理，为构建高效防污的仿生自清洁剃度防污涂层奠定坚实的科学基础。

海洋生物污损是世界各国发展海事及海洋工业面临的重大难题，目前最有效方式是涂刷海洋防污涂料，而目前环境友好型有机硅海洋防污涂料存在与基材结合力差、力学性能差、难以静水防污等缺陷问题。.本项目基于有机硅海洋防污涂料的现存瓶颈，研发丙烯酸单体改性MQ型硅树脂，利用改性有机硅聚合物实现与基材的牢固粘结，并通过改性有机硅和常见有机硅分子结构的相似性，实现最终固化涂层的多层结构机制，以此确保涂层表面低弹性，低表面自由能的防污需求。在此基础上，将惰性硅油引入弹性体中，通过硅油释放实现仿生机制的自我清洁防污效果。.本项目合成了多种改性聚硅氧烷聚合物，考察这些材料与羟基封端的聚二甲基硅氧烷树脂的分子相容性，从而筛选合适的改性材料。随后基于“相似相溶”的聚合物分子特性，构建丙烯酸密封层，改性聚硅氧烷联结层，有机硅防污层的多层结构防污涂层，而引入的苯基硅油可以从多层结构防污涂层表面析出，从而实现对静水环境中粘附污损生物的自我清洁，通过合适调控，研发了具有高效海洋防污效果的环保有机硅自清洁海洋防污涂层。