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CN-121991585-A - Self-polishing anti-fouling nano composite coating energized by natural antimicrobial arbutin and preparation method thereof

CN121991585ACN 121991585 ACN121991585 ACN 121991585ACN-121991585-A

Abstract

The invention discloses a self-polishing antifouling nano composite coating energized by natural antimicrobial arbutin and a preparation method thereof, wherein the preparation method comprises the steps of synthesizing prepolymer NPDI by aminopropyl end-capped polydimethylsiloxane and hexamethylene diisocyanate, and then reacting with hydroxyethyl acrylate to obtain an organic matrix NPDA; ZIF-8/Arb powder is prepared by adsorbing arbutin by ZIF-8, and is mixed with SiO 2 , then NPDA is added, a fluorosilicone coupling agent is added for blending reaction, and the self-polishing anti-fouling nano composite coating is prepared by spraying and drying at room temperature. The coating has the advantages of excellent mechanical property, outstanding structural stability, high lap shear strength of 14.08 MPa, hydrolysis and low surface energy, capability of realizing surface self-polishing under water flow shearing and nondestructive stripping of attached organisms, capability of improving wear resistance and durability by nano SiO 2 , capability of releasing arbutin and Zn 2+ in a targeted manner by ZIF-8/Arb in a slightly acidic environment, synergistic high-efficiency bacteriostasis and inhibition of biofilm formation, realization of long-acting active antifouling, and suitability for severe marine environments.

Inventors

  • WU WANQING
  • GUO RUIXUE
  • LI JINGTAI
  • Chen Guangluo
  • ZHENG QINGGONG

Assignees

  • 大连海事大学

Dates

Publication Date
20260508
Application Date
20260317

Claims (10)

  1. 1. The preparation method of the self-polishing anti-fouling nano composite coating energized by the natural antimicrobial agent arbutin is characterized by comprising the following steps of: S1, synthesizing an organic matrix material, namely synthesizing an aminopropyl terminated polydimethylsiloxane and hexamethylene diisocyanate to obtain a prepolymer NPDI; s2, adding hydroxyethyl acrylate into the prepolymer NPDI to obtain a polysiloxane-polyurethane acrylate polymer organic matrix material NPDA; s3, adsorbing arbutin Arb by using ZIF-8 to obtain ZIF-8/Arb powder; S4, mixing the ZIF-8/Arb powder prepared in the step S3 with SiO 2 to obtain a mixture ZIF-8/Arb/SiO 2 , adding ZIF-8/Arb/SiO 2 into the organic matrix material NPDA prepared in the step S2, mixing, adding a coupling agent triethoxy-1H, 2H-tridecafluoro-N-octyl silane, carrying out a blending reaction, and drying the obtained material at room temperature after the reaction is finished to obtain the self-polishing anti-fouling nano composite coating energized by the natural antimicrobial arbutin.
  2. 2. The method for preparing the self-polishing anti-fouling nanocomposite coating energized by arbutin as a natural antibacterial agent according to claim 1, wherein in the step S4, the mass ratio of ZIF-8/Arb powder to SiO 2 is 1:1; ZIF-8/Arb/SiO 2 is added to the organic matrix material NPDA in a proportion of 0.5-3% by mass of the organic matrix material NPDA.
  3. 3. The method for preparing the self-polishing anti-fouling nanocomposite coating energized by arbutin as a natural antibacterial agent according to claim 1, wherein in the step S4, the molar ratio of the mixture ZIF-8/Arb/SiO 2 to triethoxy-1 h,2 h-tridecafluoro-N-octylsilane is 1:1 to 1.5; the blending reaction is carried out for 2-3 hours under the stirring condition.
  4. 4. The method for preparing the self-polishing antifouling nanocomposite coating energized by arbutin as a natural antibacterial agent according to claim 1, wherein in the step S1, the specific method of the prepolymer NPDI is that the aminopropyl-terminated polydimethylsiloxane and hexamethylene diisocyanate are mixed, tetrahydrofuran as a solvent is added, and the prepolymer NPDI is prepared by stirring and reacting for 2-3 hours at a reaction temperature of 50-60 ℃ under the protection of nitrogen; the molar ratio of the aminopropyl terminated polydimethylsiloxane to the hexamethylene diisocyanate is 1:1-1.2.
  5. 5. The method for preparing a self-polishing anti-fouling nanocomposite coating energized by arbutin as a natural antibacterial agent according to claim 1, characterized in that in step S2, the molar ratio of the prepolymer NPDI to the hydroxyethyl acrylate is 1.2:1.
  6. 6. The method for preparing the self-polishing anti-fouling nano composite coating energized by the natural antibacterial agent arbutin, which is disclosed in claim 1, is characterized in that the specific step of the step S2 is that the organic matrix material NPDA is prepared by adding hydroxyethyl acrylate into a prepolymer, and stirring and reacting for 2-3 hours at 50-60 ℃ under the protection of nitrogen in a solvent tetrahydrofuran.
  7. 7. The method for preparing the self-polishing antifouling nanocomposite coating energized by arbutin as a natural antibacterial agent according to claim 1, wherein in the step S3, the antifouling functional material ZIF-8/Arb powder is prepared by the following method: Respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in a solvent, magnetically stirring until the two solutions are completely dissolved, mixing the two solutions, stirring the two solutions at room temperature for 6 hours until the solutions are milky, transferring the milky solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 10-12 hours at 60-80 ℃, separating the reaction products after the reaction is finished to obtain a solid product, and washing, drying and grinding the solid product to obtain ZIF-8 powder; and (3) placing the ZIF-8 powder into PBS (phosphate buffer solution) with the Arb concentration of 100mg/mL, magnetically stirring for 30min to finish adsorption, and then centrifuging, washing and drying the obtained suspension to obtain the anti-fouling functional substance ZIF-8/Arb powder.
  8. 8. The method for preparing a self-polishing anti-fouling nanocomposite coating energized by arbutin as a natural antibacterial agent according to claim 7, wherein in the step S3, the mass ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 1:2-2.5.
  9. 9. The method for preparing a self-polishing antifouling nanocomposite coating energized by arbutin as recited in claim 7, wherein the solvent is selected from any one of methanol and ethanol in step S3.
  10. 10. A self-polishing antifouling nanocomposite coating energized with arbutin as a natural antibacterial agent, characterized by being prepared by the preparation method of claim 1.

Description

Self-polishing anti-fouling nano composite coating energized by natural antimicrobial arbutin and preparation method thereof Technical Field The invention relates to the technical field of functional protective coatings, in particular to a self-polishing anti-fouling nano composite coating energized by natural antimicrobial arbutin and a preparation method thereof. Background The surface of an underwater hull of a ship, which is sailed in the ocean for a long time, inevitably becomes an attachment target for various marine organisms (such as barnacles, algae, shellfish, pipe worms, etc.), and this phenomenon is called marine biofouling. These marine organisms appear to be small and realistic and present a serious and costly set of problems including rapid increases in hull corrosion and maintenance costs, increased sailing resistance and surge in fuel consumption, increased greenhouse gas emissions and unnecessary energy wastage, and potentially ecological disasters of biological intrusion. Marine biofouling is therefore by no means merely a "small nuisance" to the hull surface, which is a multi-dimensional complex problem relating to marine operational safety, economic cost, energy efficiency, environmental protection and ecological safety. The application of the anti-fouling paint is a simple and effective method for solving the problem. Early widely used organotin antifouling paints (e.g., tributyltin oxide, TBT) achieve excellent antifouling effects for up to 5 years, but their persistent biotoxicity in marine environments has triggered ecological disasters. Tin-free self-polishing copolymer coatings (e.g., copper acrylate resins) as an alternative have reduced ecotoxicity, but their antifouling mechanisms are highly dependent on shear forces generated by the speed of the ship. More seriously, the current main stream of anti-fouling agent cuprous oxide (Cu 2 O) continuously releases copper ions in marine environment, and the annual global emission of the current main stream of anti-fouling agent is up to ten thousand tons. After copper ions are enriched in the sediment, the death rate of shellfish larvae can be increased and the photosynthesis of algae can be inhibited by food chain transmission. Therefore, it is necessary to develop a nanocomposite coating that combines self-polishing, high strength and integrated antifouling capabilities to meet the high efficiency, long-acting application requirements in harsh marine environments. Disclosure of Invention The invention provides a self-polishing anti-fouling nano composite coating energized by natural antimicrobial arbutin and a preparation method thereof, which aim to overcome the problems. In order to achieve the above object, the technical scheme of the present invention is as follows: the invention provides a preparation method of a self-polishing anti-fouling nano composite coating energized by natural antimicrobial arbutin, which comprises the following steps: S1, synthesizing an organic matrix material, namely synthesizing high-strength prepolymer NPDI by using aminopropyl terminated polydimethylsiloxane and hexamethylene diisocyanate; s2, adding hydroxyethyl acrylate into the prepolymer NPDI to obtain a polysiloxane-polyurethane acrylate polymer organic matrix material NPDA; s3, absorbing Arb by utilizing ZIF-8 to obtain ZIF-8/Arb powder which is a stable load and controllably released antifouling functional substance; S4, mixing the ZIF-8/Arb powder prepared in the step S3 with SiO 2 to obtain a mixture ZIF-8/Arb/SiO 2 nano-particle, adding ZIF-8/Arb/SiO 2 into the organic matrix material NPDA prepared in the step S2, mixing, adding a coupling agent triethoxy-1H, 2H-tridecafluoro-N-octyl silane, carrying out a blending reaction, obtaining the self-polishing antibacterial nano-composite material after the reaction is completed, and carrying out spray coating and room temperature drying for 72 h on the composite material to obtain the self-polishing antifouling nano-composite coating energized by the natural antibacterial agent arbutin, wherein X is the mass ratio of the ZIF-8/Arb/SiO 2 nano-particle relative to the matrix material NPDA. Further, in the step S4, the mass ratio of ZIF-8/Arb powder to SiO 2 is 1:1, ZIF-8/Arb/SiO 2 is added into the NPDA of the organic matrix material according to the mass ratio of 0.5-3% of the NPDA of the organic matrix material, and preferably ZIF-8/Arb/SiO 2 is added into the NPDA of the organic matrix material according to the mass ratio of 0.5%, 1%, 1.5%, 2% and 3% of the NPDA of the organic matrix material respectively. Further, in the step S4, the molar ratio of the mixture ZIF-8/Arb/SiO 2 to the triethoxy-1H, 2H-tridecafluoro-N-octyl silane is 1:1-1.5; the blending reaction is carried out for 2-3 hours under the stirring condition, and then the subsequent spraying and drying steps are carried out. Further, in the step S1, the prepolymer NPDI is prepared by mixing the aminopropyl terminated polydimethylsilo