目的 提高有机硅基低表面能涂层的静态防污能力和机械性能。方法 以聚四氢呋喃二醇（PTMG）与醇羟基封端聚二甲基硅氧烷（PDMS）为软段,并采用化学交联法将以席夫碱反应制备的席夫碱二醇（HPA）防污活性组分接枝到聚氨酯骨架中,制备了席夫碱二醇改性聚氨酯基低表面能防污涂层。结果 涂层的水接触角和表面能测试结果表明,引入PDMS软段后涂层的静态水接触角从(74.0±3.6)°（不含PDMS的涂层PDMS0PU）升至(103.8 ± 3.0)°（PDMS1:3PU）,表面能从45.4 mJ/m2（PDMS0PU）降至21 mJ/m2（PDMS1:2PU）,表明PDMS软段的引入能够大幅改善涂层表面润湿特性。经7天藻液浸泡后,涂层的抑制硅藻黏附率从(44.1 ±1.5)%（不含HPA的涂层PDMS1:5PU0）提升至(94.9±0.5)%（PDMS1:2PU）,硅藻相对脱附效率为(62.6± 1.1)%。贻贝对高HPA含量的涂层表现出明显趋避效果,表明该涂层在动态及静态条件下均展现出良好的防污能力。此外,形成的氨基甲酸酯结构提升了涂层耐磨损能力以及与基材间附着力（>3 MPa）。结论 席夫碱二醇改性聚氨酯涂层通过席夫碱接触杀菌与PDMS低表面能特性的协同防污机制,有效弥补了传统有机硅低表面能防污涂层在静态防污方面的不足,拓展了其在海洋防污领域的应用。
Abstract
To enhance the static fouling resistance and mechanical properties of polyurethane-based low-surface-energy coatings, it is typically necessary to incorporate modified components with specific functions to optimize their performance. Based on the formation process and principles of marine fouling organisms, the initial attachment and proliferation of bacteria are considered critical stages in the biological fouling process. Meanwhile, the biofilm structure formed by bacteria and organic matters provides favorable conditions for the subsequent adhesion and growth of large fouling organisms. Therefore, incorporating antimicrobial functional components into coating systems to inhibit biofilm formation and development has become one of the key research directions in current antifouling material development. Highly flexible PDMS segments tend to aggregate on the coating surface, significantly enhancing the material's hydrophobic properties. During coating application, mechanical stress often causes damage to the coating surface, potentially reducing its antifouling performance. Therefore, introducing polar structural units such as epoxy groups, urethane bonds, and urea groups into low-surface-energy antifouling coatings through chemical modification can effectively improve the coating's mechanical properties, thereby improving its long-term service life. The highly flexible PDMS segments tend to aggregate on the coating surface. Therefore, a Schiff base diol-modified polyurethane-based low surface energy antifouling coating was prepared with poly (tetrahydrofuran) diol and hydroxyl-terminated silicone oil as soft segments and Schiff base diol (HPA) prepared via the Schiff base reaction as the antifouling active component. To verify the synergistic antifouling mechanism between Schiff base contact killing and low surface energy of organosilicon, control samples without HPA (PDMS1:5PU0) and without PDMS soft segments (PDMS0PU) were prepared separately. Following the introduction of PDMS soft segments, the segments became enriched with hydrophobic methyl (—CH3) groups. Concurrently, the Si—O—Si structure in the main chain exhibited high segmental freedom, enabling enrichment at the interface. This conferred excellent hydrophobic properties to the coating, achieving a static water contact angle of (103.8±3.0)°. Benefiting from the inherent low surface energy of PDMS segments, the surface energy of the PDMSXPU coating ranged between 21.0 and 25.2 mJ/m2. After being immersed in artificial seawater for 7 days, the coated samples maintained structural integrity with no noticeable changes observed, indicating that this coating system exhibited stability in marine environments and possessed reliable long-term service performance. After 72 hours of immersion in diatom solution, the coating inhibited diatom attachment by (94.9±0.5)% and exhibited a relative diatom detachment efficiency of (62.6±1.1)%. Mussels showed a pronounced repellent effect toward coatings with high HPA content, indicating that the coating demonstrated excellent antifouling performance under both dynamic and static conditions. In summary, the incorporation of PDMS enhances the coating's hydrophobicity and improves its dynamic antifouling performance, while HPA ensures its static antifouling capability. Furthermore, the introduction of carbamate groups increases the coating's abrasion resistance and adhesion to the substrate (>3 MPa). The Schiff base diol-modified polyurethane coating exhibits a synergistic antifouling mechanism through Schiff base contact killing and the low surface energy properties of PDMS. This advancement expands its application in marine antifouling technology.
关键词
海洋防污 /
有机硅 /
低表面能涂层 /
聚氨酯 /
席夫碱
Key words
marine antifouling /
silicone resin /
low surface energy coating /
polyurethane /
Schiff base
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