Synthesis and Antifouling Performance of Schiff Base Diol Modified Polyurethane

ZHANG Kai; LIU Silei; GUI Taijiang; CHEN Rongrong

doi:10.16490/j.cnki.issn.1001-3660.2026.04.006

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Surface Technology ›› 2026, Vol. 55 ›› Issue (4) : 64-73. DOI: 10.16490/j.cnki.issn.1001-3660.2026.04.006

Corrosion and Protection

Synthesis and Antifouling Performance of Schiff Base Diol Modified Polyurethane

ZHANG Kai¹, LIU Silei², GUI Taijiang¹, CHEN Rongrong^2,*

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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 (PDMS_1:5PU₀) 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 PDMS_XPU 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.

Key words

marine antifouling / silicone resin / low surface energy coating / polyurethane / Schiff base

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ZHANG Kai, LIU Silei, GUI Taijiang, CHEN Rongrong. Synthesis and Antifouling Performance of Schiff Base Diol Modified Polyurethane[J]. Surface Technology. 2026, 55(4): 64-73

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