生物响应性壳聚糖基自抛光树脂的合成及其海洋防污性能研究

Marine biofouling has been a significant challenge for ship building and marine engineering, while tin-free self-polishing antifouling coating with hydrolysis features of based polymer in seawater is the most widely used approach to solve this problem. However, the self-polishing coatings could not cope with variable fouling situations because of their stable erosion rate. In this project, we propose a novel antifouling coating which could auto-regulate its erosion rate according to the fouling level through the biological response of natural biodegradable chitosan. Graft copolymers of chitosan and poly (acrylate) self-polishing polymers are mainly studied and the auto-regulated erosion rate coatings based on them are prepared. The project goes on to establish and understand internal relations between main and side chain structure, molecule weight and matrix degradation rate, as well as clarify the degradation pathway of these hydrolysis/degradation co-regulated graft copolymers and finally discuss the antifouling mechanism of the synthetic biological response self-polishing coatings by the combination of lab scale simulated degradation and seawater immersion tests. These achievements are expected to provide theoretical and technological foundation for the development of innovative antifouling coatings.

海洋生物污损是船舶装备及海洋工程面临的重大难题，基于树脂水解原理的无锡自抛光防污漆是目前解决这一问题的主要手段。本研究针对传统自抛光防污漆磨蚀速率固定、多变环境下抗污性不佳的问题，根据天然壳聚糖对海洋生物的响应性，创新性地提出一种利用生物污损程度调控防污涂层降解/水解速率的研究思路。研究重点探讨天然高分子壳聚糖与丙烯酸酯类自抛光树脂接枝共聚物的构建方法，制备以此为基体的新型生物响应型防污涂层，探讨接枝共聚树脂主侧链结构、分子量对树脂降解速率的影响，结合实验室模拟降解试验及海水浸泡试验，解析水解/降解共调控的接枝共聚树脂的降解规律及途径，探讨具有生物响应性壳聚糖基自抛光树脂的的防污机理，为制备新型智能防污涂层提供理论和技术基础。

海洋生物污损会引发舰船航行阻力、燃油消耗增加及船底腐蚀加速等多重危害，并带来高额经济损失。涂覆含铜的海洋防污涂层是目前解决海洋生物污损问题最经济有效的策略之一。然而，随着国家生态文明建设战略的不断推进，寻求高效、环境友好的防污涂层技术具有非常重要的意义。本研究通过聚合物分子结构设计及合成工艺研究分别合成了不同组成结构的丙烯酸硅烷酯树脂、丙烯酸硼系树脂及壳聚糖接枝丙烯酸酯共聚物系列材料。研究通过调节功能性单体比例及合成工艺提高了丙烯酸硅烷自抛光防污涂料的实海防污性能和期效，所制备的丙烯酸硅烷酯树脂基涂层具有至少11个月的实海静态防污效果。设计合成的丙烯酸氟硼自抛光树脂具有较低的抛光速率及两亲性，使涂层具有较好的抗海藻防污特性。另一方面，利用壳聚糖的两个活性位点，成功对壳聚糖进行了防污官能化，并制备了丙烯酸接枝壳聚糖共聚物，实现涂层在海水及藻液中的失重差异，使涂层具有一定的抑菌和抗蛋白吸附效果。通过本项目的实施掌握了不同丙烯酸酯类复合树脂结构在海水及污损环境下的磨蚀情况，为将来深入研究污损生物与材料之间的选择响应奠定基础。