Self-adaptive phase-change microstructure antibacterial antifouling coating as well as preparation method and application thereof
By using an adaptive phase change microstructure antibacterial and antifouling coating, which combines reversible phase change units and antibacterial groups, the contradiction between flexibility and stability in biomimetic coatings is resolved, achieving an adaptive antifouling effect in complex environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- QUZHOU RES INST OF ZHEJIANG UNIV
- Filing Date
- 2026-01-08
- Publication Date
- 2026-04-10
AI Technical Summary
Existing biomimetic coatings struggle to balance flexibility and antifouling properties with structural stability, resulting in a trade-off between antifouling performance and durability. Furthermore, the performance of traditional silicone coatings degrades under low flow rate conditions.
An adaptive phase change microstructure antibacterial and antifouling coating is adopted. By introducing reversible phase change units and photothermal conversion fillers, the material enters a low modulus oscillation state under high temperature or strong light. Combined with antibacterial groups, dynamic modulus regulation is achieved to adapt to complex environments.
Under high temperature or strong light conditions, the coating modulus decreases, and the microstructure oscillation inhibits dirt adhesion; under low temperature or dark conditions, the modulus increases, improving durability and achieving adaptive anti-fouling, making it suitable for long-term anti-fouling in various environments.
Smart Images
Figure CN121825409A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of antibacterial and antifouling materials and surface and interface functional materials, and relates to an adaptive phase change microstructure antibacterial and antifouling coating, its preparation method and application. Background Technology
[0002] In marine and freshwater environments, bacteria, algae, barnacles, shellfish, and other organisms easily adhere to the surfaces of equipment and ship hulls, forming biofouling layers that lead to increased drag, higher energy consumption, equipment blockage, and shortened lifespan. The International Maritime Organization (IMO) has banned the use of tributyltin-based organotin antifouling agents, making non-toxic and environmentally friendly antifouling coatings a research hotspot. Current mainstream solutions include self-polishing and silicone-based fouling-removing coatings. Silicone coatings are widely used due to their low surface energy and environmental friendliness, but their antifouling mechanism relies on high-speed water flow, resulting in a significant performance degradation in low-flow-rate environments.
[0003] To overcome this limitation, biomimetic strategies have attracted attention. In nature, organisms such as corals and sea cucumbers achieve antifouling through the periodic swaying of flexible tentacles or surface microstructures, effectively inhibiting adhesion even in static environments. However, existing biomimetic coatings are mostly fixed-modulus materials, making it difficult to balance flexible antifouling with structural stability, resulting in a contradiction between antifouling performance and durability.
[0004] In recent years, the combination of photo / thermal responsive phase change materials and antibacterial organosilicon materials has provided a new approach to achieving adaptive antifouling. This patent introduces reversible phase change units and photothermal conversion fillers, enabling the material to enter a low-modulus oscillation state under high temperature or strong light, and recover a high modulus under low temperature or dark environments, thus improving durability; simultaneously, the antibacterial groups can inhibit initial microbial adhesion. This comprehensive strategy of "low surface energy + antibacterial + dynamic modulus regulation" is not only applicable to marine and freshwater antifouling, but can also be extended to the surfaces of medical catheters, artificial joints, and other devices that require inhibition of biofilm formation, providing a new technical path for long-term antifouling in multiple environments. Summary of the Invention
[0005] The purpose of this invention is to overcome the shortcomings and deficiencies of existing solutions and to provide an adaptive phase change microstructure antibacterial and antifouling coating and its preparation method.
[0006] The solution of the present invention is as follows: On the one hand, this invention proposes a method for preparing an adaptive phase change microstructure antibacterial and antifouling coating, comprising the following steps: (1) Synthesis of antibacterial active silane functional units Triclosan was dissolved in dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis, and the product was washed and purified to obtain acrylate-based triclosan antibacterial monomers. Hydroxy-4-methylcoumarin was dissolved in dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis, and the product was washed and purified to obtain acrylate-based coumarin antibacterial monomers. acrylate-based triclosan antibacterial monomers and / or acrylate-based coumarin antibacterial monomers were dissolved in tetrahydrofuran, and mercaptopropyltriethoxysilane was used as a chain transfer agent. An initiator was added, and the reaction was carried out at 60°C under a nitrogen atmosphere for 10 hours. The product was washed and purified to obtain antibacterial active silane functional units.
[0007] (2) Synthesis of phase change type active silane functional units Alkyl acrylate was dissolved in tetrahydrofuran, and an appropriate amount of mercaptopropyltriethoxysilane and an initiator were added. The mixture was reacted at 60°C under a nitrogen atmosphere for 10-24 hours. After washing and purification, the phase change active silane functional unit was obtained.
[0008] (3) Synthesis of antibacterial organosilicon resin with phase change function Antibacterial active silane functional units, phase change active silane functional units, silanol-terminated polydimethylsiloxane and tetraethoxysilane were dissolved in ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize antibacterial organosilicon resin with phase change function.
[0009] (4) Preparation of antibacterial and antifouling coating of composite array microstructure Nanofillers were added to an antibacterial silicone resin with phase change function and mixed evenly to obtain a composite prepolymer. The obtained composite prepolymer was poured into a template with a pore array. After removing air bubbles, the prepolymer was cured and demolded to obtain an adaptive phase change microstructure antibacterial and antifouling coating.
[0010] Preferably, the molecular structure of the antibacterial active silane functional unit is as follows: ; Where x = 1 - 100, y = 1 - 100.
[0011] Preferably, the molecular structure of the phase change type active silane functional unit is as follows: ; Where z = 10-500, m = 8-18, and the value of m determines the type of alkyl group.
[0012] Preferably, the molecular structure of the antibacterial organosilicon resin with phase change function is as follows: .
[0013] Preferably, the molecular weight of the silanol-terminated polydimethylsiloxane in step (3) is 500-10000.
[0014] Preferably, the nanofiller in step (4) is any one or a combination of several of the following: carbon nanoparticles, carbon nanotubes, graphene, molybdenum disulfide, and MXene.
[0015] Preferably, the initiator in steps (1) and (2) is one of azobisisobutyronitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and azobisisoheptanenitrile.
[0016] Preferably, the microstructure can be an array composed of one or more of the following: circular, polygonal, irregular polygonal, conical, and mushroom-shaped; the size of a single structure is: projected diameter 10-30000 micrometers, aspect ratio 3-0.5.
[0017] On the other hand, this invention also proposes an adaptive phase-change microstructure antibacterial and antifouling coating prepared by the above-mentioned method. In this invention, the coating is made by compositing an antibacterial organosilicon resin with phase-change function with nanofillers and then forming an array of microstructures. The coating undergoes a reversible phase change within an adjustable temperature range, causing its modulus to dynamically switch between high and low modulus states: under high temperature or strong light conditions, the modulus decreases, and the microstructure produces a large amplitude oscillation, thereby inhibiting dirt adhesion; under low temperature or dark environments, the modulus increases, the microstructure stabilizes, and durability is improved. Through a phase-change-driven modulus regulation mechanism, adaptive antifouling in complex environments is achieved.
[0018] Preferably, the organosilicon resin is a resin with a three-dimensional network structure obtained by hydrolysis and polycondensation of monomers comprising antibacterial active silane functional units, phase change active silane functional units, silanol-terminated polydimethylsiloxane, and tetraethoxysilane. The antibacterial active silane functional units are polymer chains with antibacterial groups derived from triclosan and / or coumarin derivatives branched on the sides and hydrolyzable silaneoxy groups at the ends; the phase change active silane functional units are polymer chains with long-chain alkyl groups branched on the sides and hydrolyzable silaneoxy groups at the ends.
[0019] This invention also proposes the application of the aforementioned adaptive phase change microstructure antibacterial and antifouling coating on the surfaces of ship hulls, offshore platforms, heat exchangers, seawater or freshwater pipelines, water treatment equipment, medical catheters, artificial joints, implantable devices, or biomaterials.
[0020] Compared with the prior art, the beneficial effects of the present invention are: This invention first constructs a triclosan or coumarin-based synergistic antibacterial unit, then prepares a long-chain alkyl phase-change functional unit, followed by the preparation of an organosilicon resin through polycondensation. Finally, an array microstructure coating is obtained by molding the organosilicon resin with nanofillers using a template method. The advantages of this invention are that the modulus of the microstructure decreases under high temperature or strong light conditions, resulting in large amplitude oscillations and thus inhibiting fouling adhesion; under low temperature or dark environments, the modulus increases, the microstructure stabilizes, and durability is improved. By coupling the antibacterial unit, microstructure, and low surface energy characteristics of organosilicon through a phase-change driven modulus regulation mechanism, adaptive antifouling in complex environments is achieved, exhibiting broad-spectrum antifouling properties. Attached Figure Description
[0021] Figure 1 This is a schematic diagram of a representative array microstructure of Embodiment 1 of the present invention. Detailed Implementation
[0022] The invention will be further described in detail below with reference to specific embodiments. These embodiments will enable those skilled in the art to gain a more comprehensive understanding of the invention.
[0023] The following are three specific embodiments and three comparative examples:
[0024] Example 1: (x=20, y=20, z=50, m=12) This embodiment relates to an adaptive phase change microstructure antibacterial and antifouling coating and its preparation method as follows: Step 1: Synthesis of antibacterial active silane functional units 14.5 g of triclosan was dissolved in 40 mL of dichloromethane, and 4.5 mL of acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based triclosan antibacterial monomers were obtained. 8.8 g of hydroxy-4-methylcoumarin was dissolved in 40 mL of dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based coumarin antibacterial monomers were obtained. 68.6 g of acrylate-based triclosan antibacterial monomers and 46 g of acrylate-based coumarin antibacterial monomers were dissolved in 200 mL of tetrahydrofuran, and 1.96 g of mercaptopropyltriethoxysilane and 50 mg of azobisisobutyronitrile were added. The reaction was carried out at 60 °C under a nitrogen atmosphere for 24 hours. After washing and purification, antibacterial active silane functional units were obtained.
[0025] Step 2 Synthesis of Phase Change Type Active Silane Functional Units 107g of tetradecyl acrylate was dissolved in 200mL of tetrahydrofuran, and 1.96g of mercaptopropyltriethoxysilane and 50mg of azobisisobutyronitrile were added. The mixture was reacted at 60 °C for 10 hours under a nitrogen atmosphere. After washing and purification, the phase change active silane functional unit was obtained.
[0026] Step 3: Synthesis of antibacterial organosilicon resin with phase change function 1g of antibacterial active silane functional unit, 1g of phase change active silane functional unit, 10g of silanol-terminated polydimethylsiloxane (molecular weight 2000) and 0.5g of tetraethoxysilane were dissolved in 100mL of ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize antibacterial organosilicon resin with phase change function.
[0027] Step 4: Preparation of antibacterial and antifouling coating of composite array microstructure 0.5 wt% nano-carbon powder was added to an antibacterial silicone resin with phase change function. After uniform mixing, the composite prepolymer was cast into a template with a porous array. After removing air bubbles, the mixture was cured and demolded to obtain an adaptive microstructure antibacterial and antifouling coating. Figure 1 As shown, the projected diameter of a single cone structure in the conical array is 300 micrometers, and the aspect ratio is 3.
[0028] Example 2: (x=30, y=10, z=50, m=14) This embodiment relates to an adaptive phase change microstructure antibacterial and antifouling coating and its preparation method as follows: Step 1: Synthesis of antibacterial active silane functional units 14.5 g of triclosan was dissolved in 40 mL of dichloromethane, and 4.5 mL of acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based triclosan antibacterial monomers were obtained. 8.8 g of hydroxy-4-methylcoumarin was dissolved in 40 mL of dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based coumarin antibacterial monomers were obtained. 45.7 g of acrylate-based triclosan antibacterial monomers and 23 g of acrylate-based coumarin antibacterial monomers were dissolved in 200 mL of tetrahydrofuran, and 1.96 g of mercaptopropyltriethoxysilane and 50 mg of azobisisobutyronitrile were added. The reaction was carried out at 60 °C under a nitrogen atmosphere for 24 hours. After washing and purification, antibacterial active silane functional units were obtained.
[0029] Step 2 Synthesis of Phase Change Type Active Silane Functional Units 139g of hexadecyl acrylate was dissolved in 200mL of tetrahydrofuran, and 1.96g of mercaptopropyltriethoxysilane and 50mg of azobisisobutyronitrile were added. The mixture was reacted at 60°C under a nitrogen atmosphere for 10 hours. After washing and purification, the phase change active silane functional unit was obtained.
[0030] Step 3: Synthesis of antibacterial organosilicon resin with phase change function 1.2g of antibacterial active silane functional unit, 1g of phase change active silane functional unit, 10g of silanol-terminated polydimethylsiloxane (molecular weight 2500) and 0.5g of tetraethoxysilane were dissolved in 100mL of ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize an antibacterial organosilicon resin with phase change function.
[0031] Step 4: Preparation of antibacterial and antifouling coating of composite array microstructure 0.5 wt% nano-carbon powder was added to an antibacterial silicone resin with phase change function. After uniform mixing, the composite prepolymer was cast into a template with a porous array. After removing air bubbles, the mixture was cured and demolded to obtain an adaptive microstructure antibacterial and antifouling coating. Figure 1 As shown, the projected diameter of a single cone structure in the conical array is 300 micrometers, and the aspect ratio is 3.
[0032] Example 3: (x=10, y=30, z=30, m=14) This embodiment relates to an adaptive phase change microstructure antibacterial and antifouling coating and its preparation method as follows: Step 1: Synthesis of antibacterial active silane functional units 14.5 g of triclosan was dissolved in 40 mL of dichloromethane, and 4.5 mL of acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based triclosan antibacterial monomers were obtained. 8.8 g of hydroxy-4-methylcoumarin was dissolved in 40 mL of dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based coumarin antibacterial monomers were obtained. 22.8 g of acrylate-based triclosan antibacterial monomers and 69 g of acrylate-based coumarin antibacterial monomers were dissolved in 200 mL of tetrahydrofuran, and 1.96 g of mercaptopropyltriethoxysilane and 50 mg of azobisisobutyronitrile were added. The reaction was carried out at 60 °C under a nitrogen atmosphere for 24 hours. After washing and purification, antibacterial active silane functional units were obtained.
[0033] Step 2 Synthesis of Phase Change Type Active Silane Functional Units 83.4 g of hexadecyl acrylate was dissolved in 200 mL of tetrahydrofuran, and 1.96 g of mercaptopropyltriethoxysilane and 50 mg of azobisisobutyronitrile were added. The mixture was reacted at 60 °C for 10 hours under a nitrogen atmosphere. After washing and purification, the phase change active silane functional unit was obtained.
[0034] Step 3: Synthesis of antibacterial organosilicon resin with phase change function 1.2g of antibacterial active silane functional unit, 1.2g of phase change active silane functional unit, 10g of silanol-terminated polydimethylsiloxane (molecular weight 2500) and 0.5g of tetraethoxysilane were dissolved in 100mL of ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize an antibacterial organosilicon resin with phase change function.
[0035] Step 4: Preparation of antibacterial and antifouling coating of composite array microstructure 0.6 wt% nano-carbon powder was added to an antibacterial silicone resin with phase change function. After uniform mixing, the composite prepolymer was cast into a template with a porous array. After removing air bubbles, the mixture was cured and demolded to obtain an adaptive microstructure antibacterial and antifouling coating. Figure 1 As shown, the projected diameter of a single cone structure in the conical array is 300 micrometers, and the aspect ratio is 3.
[0036] Comparative Example 1: (No antibacterial component) The preparation and application methods of the coatings involved in this comparative example are as follows: Step 1: Synthesis of Phase Change Type Active Silane Functional Units 107g of tetradecyl acrylate was dissolved in 200mL of tetrahydrofuran, and 1.96g of mercaptopropyltriethoxysilane and 50mg of azobisisobutyronitrile were added. The mixture was reacted at 60 °C for 10 hours under a nitrogen atmosphere. After washing and purification, the phase change active silane functional unit was obtained.
[0037] Step 2 Synthesis of organosilicon resin with phase change function 1g of phase change active silane functional unit, 10g of silanol-terminated polydimethylsiloxane (molecular weight 2000) and 0.5g of tetraethoxysilane were dissolved in 100mL of ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize an antibacterial organosilicon resin with phase change function.
[0038] Step 3: Preparation of antibacterial and antifouling coating of composite array microstructure 0.5 wt% nano-carbon powder was added to a silicone resin with phase change function. After uniform mixing, the composite prepolymer was cast into a template with a porous array. After removing air bubbles, the mixture was cured and demolded to obtain an adaptive microstructure antibacterial and antifouling coating. Figure 1 As shown, the projected diameter of a single cone structure in the conical array is 300 micrometers, and the aspect ratio is 3.
[0039] Comparative Example 2: (Elementary Units Without Phase Transition) The preparation and application methods of the coatings involved in this comparative example are as follows: Step 1: Synthesis of antibacterial active silane functional units 14.5 g of triclosan was dissolved in 40 mL of dichloromethane, and 4.5 mL of acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based triclosan antibacterial monomers were obtained. 8.8 g of hydroxy-4-methylcoumarin was dissolved in 40 mL of dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based coumarin antibacterial monomers were obtained. 68.6 g of acrylate-based triclosan antibacterial monomers and 46 g of acrylate-based coumarin antibacterial monomers were dissolved in 200 mL of tetrahydrofuran, and 1.96 g of mercaptopropyltriethoxysilane and 50 mg of azobisisobutyronitrile were added. The reaction was carried out at 60 °C under a nitrogen atmosphere for 24 hours. After washing and purification, antibacterial active silane functional units were obtained.
[0040] Step 2 Synthesis of antibacterial silicone resin 1g of antibacterial active silane functional unit, 10g of silanol-terminated polydimethylsiloxane (molecular weight 2000) and 0.5g of tetraethoxysilane were dissolved in 100mL of ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize antibacterial organosilicon resin with phase change function.
[0041] Step 3: Preparation of antibacterial and antifouling coating of composite array microstructure 0.5 wt% nano-carbon powder was added to an antibacterial silicone resin and mixed thoroughly. The composite prepolymer was then cast into a template with a porous array. After removing air bubbles, the mixture was cured and demolded to obtain an adaptive microstructure antibacterial and antifouling coating. Figure 1 As shown, the projected diameter of a single cone structure in the conical array is 300 micrometers, and the aspect ratio is 3.
[0042] Comparative Example 3: (No microstructure) The preparation and application methods of the coatings involved in this comparative example are as follows: Step 1: Synthesis of antibacterial active silane functional units 14.5 g of triclosan was dissolved in 40 mL of dichloromethane, and 4.5 mL of acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based triclosan antibacterial monomers were obtained. 8.8 g of hydroxy-4-methylcoumarin was dissolved in 40 mL of dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out for 8 hours under triethylamine base catalysis. After washing and purification, acrylate-based coumarin antibacterial monomers were obtained. 68.6 g of acrylate-based triclosan antibacterial monomers and 46 g of acrylate-based coumarin antibacterial monomers were dissolved in 200 mL of tetrahydrofuran, and 1.96 g of mercaptopropyltriethoxysilane and 50 mg of azobisisobutyronitrile were added. The reaction was carried out at 60 °C under a nitrogen atmosphere for 24 hours. After washing and purification, antibacterial active silane functional units were obtained.
[0043] Step 2 Synthesis of Phase Change Type Active Silane Functional Units 107g of tetradecyl acrylate was dissolved in 200mL of tetrahydrofuran, and 1.96g of mercaptopropyltriethoxysilane and 50mg of azobisisobutyronitrile were added. The mixture was reacted at 60°C under a nitrogen atmosphere for 10 hours. After washing and purification, the phase change active silane functional unit was obtained.
[0044] Step 3: Synthesis of antibacterial organosilicon resin with phase change function 1g of antibacterial active silane functional unit, 1g of phase change active silane functional unit, 10g of silanol-terminated polydimethylsiloxane (molecular weight 2000) and 0.5g of tetraethoxysilane were dissolved in 100mL of ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize antibacterial organosilicon resin with phase change function.
[0045] The products prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to a six-month real-sea antifouling test on the cladding panels. The results are shown in Table 1.
[0046] Table 1. Evaluation results of the actual sea-based gabion panels of the embodiments and comparative examples of the present invention.
[0047] In summary, comparing Examples 1-3 with Comparative Example 1, the lack of antibacterial active silane functional units resulted in a biofouling rate of 10.5%, indicating the beneficial antibacterial and antifouling effects of the antibacterial active silane functional units. Comparative Example 2, an organosilicon microstructure antifouling surface without phase-change active silane functional units, showed a significant increase in biofouling rate to 7.3%, demonstrating the beneficial antibacterial and antifouling effects of the phase-change active silane functional units. Comparative Example 3, an organosilicon antifouling surface without microstructures, showed an increase in biofouling rate to 8.5%, indicating the beneficial antibacterial and antifouling effects of the array microstructures. Therefore, through multiple comparisons, organosilicon surfaces that simultaneously possess antibacterial, phase-change, and array microstructure functions exhibit superior antibacterial and antifouling performance.
[0048] In summary, the technical solution of the present invention has the following advantages: (1) By introducing thermal / optical responsive phase transition units, the coating modulus can be intelligently switched according to environmental conditions. The low modulus state under high temperature / strong light causes the microstructure to oscillate and actively repel fouling organisms; the high modulus state under low temperature / dark environment maintains structural stability, thereby improving the environmental adaptability and service life of the coating. (2) Innovatively, the three major mechanisms of "dynamic physical antifouling (microstructure oscillation)", "active chemical antibacterial (triclosan / coumarin)" and "passive low surface energy antifouling (organosilicon matrix)" are coupled into a single coating system, forming a comprehensive antifouling barrier with synergistic effect, a wide antifouling spectrum and long-lasting effect; (3) It avoids the use of toxic antifouling agents and adopts relatively environmentally friendly raw materials and preparation processes. The preparation method is mature and can achieve large-area, regular microstructure coating through template method, which has good industrialization prospects.
[0049] (4) It is not only applicable to traditional marine antifouling fields that require high-speed water flow, but also shows great application potential in static or low-flow freshwater systems, medical implants and other occasions.
[0050] The parts of this invention not covered are the same as or implemented using existing technology.
[0051] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention's specification and drawings, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.
Claims
1. A method for preparing an adaptive phase change microstructure antibacterial and antifouling coating, characterized in that, Includes the following steps: Step 1: Synthesis of antibacterial active silane functional units Triclosan was dissolved in dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out under triethylamine base catalysis, and the product was purified by washing to obtain acrylate-based triclosan antibacterial monomers. Hydroxy-4-methylcoumarin was dissolved in dichloromethane, and acryloyl chloride was added dropwise under ice bath conditions. The reaction was carried out under triethylamine base catalysis, and the product was purified by washing to obtain acrylate-based coumarin antibacterial monomers. The acrylate-based triclosan antibacterial monomers and / or acrylate-based coumarin antibacterial monomers were dissolved in tetrahydrofuran, and mercaptopropyltriethoxysilane was used as a chain transfer agent. An initiator was added, and the reaction was carried out under a nitrogen atmosphere. The product was purified by washing to obtain antibacterial active silane functional units. Step 2: Synthesis of phase-change active silane functional units Alkyl acrylate was dissolved in tetrahydrofuran, and an appropriate amount of mercaptopropyltriethoxysilane and an initiator were added. The reaction was carried out under a nitrogen atmosphere, and the phase change type active silane functional unit was obtained after washing and purification. Step 3: Synthesis of antibacterial organosilicon resin with phase change function Antibacterial active silane functional units, phase change active silane functional units, silanol-terminated polydimethylsiloxane and tetraethoxysilane are dissolved in ethyl acetate and polycondensed under the action of dibutyltin diacetate catalyst to synthesize antibacterial organosilicon resin with phase change function. Step 4: Preparation of antibacterial and antifouling coating of composite array microstructure Nanofillers were added to an antibacterial silicone resin with phase change function and mixed evenly to obtain a composite prepolymer. The obtained composite prepolymer was poured into a template with a pore array. After removing air bubbles, the prepolymer was cured and demolded to obtain an adaptive phase change microstructure antibacterial and antifouling coating.
2. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The molecular structure of the antibacterial active silane functional unit is as follows: ； Where x = 1 - 100, y = 1 - 100.
3. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The molecular structure of the phase-change active silane functional unit is as follows: ； Where z = 10-500, m = 8-18.
4. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The molecular structure of the antibacterial silicone resin with phase change function is as follows: 。 5. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The molecular weight of the silanol-terminated polydimethylsiloxane described in step 3 is 500-10000.
6. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The nanofiller mentioned in step 4 is any one or a combination of several of the following: carbon nanoparticles, carbon nanotubes, graphene, molybdenum disulfide, and MXene.
7. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The initiator mentioned in steps 1 and 2 is one of azobisisobutyronitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and azobisisoheptanenitrile.
8. The method for preparing the adaptive phase change microstructure antibacterial and antifouling coating according to claim 1, characterized in that, The microstructure is an array composed of one or more of the following: circular, polygonal, irregular polygonal, conical, and mushroom-shaped; the size of a single structure is: projected diameter 10-30000 micrometers, aspect ratio 3-0.
5.
9. An adaptive phase change microstructure antibacterial and antifouling coating, prepared by the method described in any one of claims 1-8, characterized in that, The coating is made by combining an antibacterial silicone resin with phase change function with nanofillers to form an array microstructure. The coating can undergo a reversible phase change within an adjustable temperature range, allowing its modulus to dynamically switch between high and low states: under high temperature or strong light conditions, the modulus decreases, and the microstructure produces a large amplitude oscillation, thereby inhibiting dirt adhesion; under low temperature or dark environments, the modulus increases, the microstructure stabilizes, and durability is improved; through a phase change-driven modulus regulation mechanism, adaptive antifouling in complex environments is achieved; the silicone resin is a resin with a three-dimensional network structure obtained by hydrolysis and polycondensation reaction of monomers containing antibacterial active silane functional units, phase change active silane functional units, silanol-terminated polydimethylsiloxane, and tetraethoxysilane.
10. The application of the adaptive phase change microstructure antibacterial and antifouling coating as described in claim 9 on the surfaces of ship hulls, offshore platforms, heat exchangers, seawater or freshwater pipelines, water treatment equipment, medical catheters, artificial joints, implantable devices or biomaterials.