环境友好的BIT/丙烯酸酯自抛光海洋防污涂料的制备及性能研究

There are great damages of marine biofouling to mankind marine business activities. Recently, for the prevention of the marine fouling organisms, the widely used of organic tin and cuprous oxide antifouling paints have serious harm to the algae and fish and other marine creatures. Along with the increasing attention to the marine ecological environment, it is important to developing excellent marine antifouling coatings with low-toxicity, high-efficient and environmentally friendly properties for the protection of the Marine environment.. The environment friendly 1-2-benzisothiazol-3-one (BIT) derivatives were selected as the research objectives in this topic. The compounds with favorable bacteria and algal inhibiting activities will be closed and be prepared to polymerizable monomers by introduced a vinyl in the molecular structures. The acrylate prepolymers with BIT units on side chain would be designed and synthesized by the copolymerized of BIT monomers with acrylic esters. The acrylic marine antifouling coatings with BIT function group on side chain would be prepared through the reaction of the prepolymer with organic acid zinc. The structure characteristics, hydrolysis performance, BIT release rate and marine antifouling properties, as well as the structure-activity relationships of the functional coatings would be studied. . The key technologies for the preparation of the functional self-polishing antifouling paints would be mastered, and the marine environmental pollution problems duo to the large releasing of tin and cuprous oxide from antifouling paint would be avoided. And a series of green marine antifouling coatings with excellent antifouling and antibacterial properties would be obtained for the reduction of the marine pollution and the protection of the marine ecological environment.

海洋生物污损给人类海洋活动带来了严重的危害，近年来大量使用有机锡和氧化亚铜涂料防止海洋污损生物，对海洋藻类和鱼类等生物带来了严重的危害。随着人们对生态环境的日益重视，研究高效、低毒、绿色的海洋防污涂料，对保护海洋环境有重要的意义。. 本项目以环境友好的防污杀菌化合物1,2-苯并异噻唑啉-3-酮（BIT）为研究目标，选择杀菌抑藻活性良好的结构体系，在BIT分子中引入双键结构制备成可聚单体，与丙烯酸酯共聚，合成侧链接枝BIT功能结构的丙烯酸酯预聚物，再与有机酸锌反应，制备成BIT功能化的丙烯酸锌防污涂料。研究涂料的结构特征、水解性能、BIT释放性能及海洋防污性能，研究聚合物结构与防污性能之间的关系。掌握制备此类接枝型自抛光防污涂料的关键技术，解决现有防污涂料中于氧化亚铜的大量释放而带来的海洋环境污染问题。获得具有优良防污、杀菌性能的绿色海洋防污涂料，减少海洋污染，保护海洋生态环境。

海洋生物污损对海洋运输和海岸设施造成了严重的危害。目前，防止海洋生物污损的主要途径是在船体和海洋结构物表面涂刷防污涂料。而现有的有机锡和Cu2O防污涂料的使用，会对海洋生态环境造成严重的污染。因此，设计、合成结构新颖的高效、无毒、无残留的防污涂料，成为未来海洋防污涂料的重要发展方向，对人们保护海洋生态环境具有重要的意义。. 本课题拟设计合成一种侧链接枝BIT化合物的聚丙烯酸酯类无铜海洋防污涂料。以BIT小分子化合物的为基础，设计合成具有自抛光特性的接枝BIT侧链的丙烯酸锌海洋防污涂料（图1）。研究聚合物结构与防污性能之间的关系，掌握制备此类接枝型可降解聚合物防污涂料的关键技术，解决现有防污涂料中由于氧化亚铜的不断释放而带来的环境污染问题，减少海洋污染，实现海洋可持续发展。. 该项目已合成的单体化合物有：2-(苯并异噻唑啉-3-酮-2-基)甲酸丙烯酯、2-(苯并异噻唑啉-3-酮-2-基)丙烯酮、苯并异噻唑啉酮乙酸锌、BIT-甲酸-2-丁烯酯、BIT-甲酸-S-丙烯硫醇酯、BIT-甲酸烯丙基胺、BIT-甲酸-N-甲基烯丙基胺、BIT-丙烯氧基三嗪；该项目已合成的接枝型防污树脂有：BIT-甲酸丙烯酯的丙烯酸树脂、2-(苯并异噻唑啉-3-酮-2-基)丙烯酮的丙烯酸树脂、BIT乙酸锌丙烯酸树脂、BIT-甲酸-2-丁烯酯的丙烯酸树脂、BIT-甲酸丙烯硫醇酯的丙烯酸树脂、BIT-甲酸丙烯酰胺的丙烯酸树脂、BIT-甲酸-N-甲基丙烯酰胺的丙烯酸树脂、BIT-丙烯氧基三嗪丙烯酸锌树脂、BIT-丙烯氧基三嗪-杂环-丙烯酸树脂等9支接枝型聚合物树脂。通过IR、1H NMR等手段测试了单体的结构。并测试了共聚物的官能团、分子量分布、水解性能、剥蚀速度、抑菌抑藻性能和海洋防污性能。