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CN-118496729-B - Surface sulfonated organosilicon hydrogel antifouling coating and preparation method thereof

CN118496729BCN 118496729 BCN118496729 BCN 118496729BCN-118496729-B

Abstract

The invention belongs to the field of marine antifouling, and in particular relates to a surface sulfonated organosilicon hydrogel antifouling coating and a preparation method thereof. The coating is obtained by soaking an organosilicon hydrogel coating in a solution of hydroxyl and sulfonic acid group-containing organic matters for surface sulfonation treatment, wherein the mass concentration of the hydroxyl and sulfonic acid group-containing organic matters in the solution of the hydroxyl and sulfonic acid group-containing organic matters is 0.01-0.1 g/mL. According to the surface sulfonated organosilicon hydrogel antifouling coating, a material surface with a hydration layer, electronegativity and low surface energy synergistic antifouling effect is constructed, and the prepared antifouling coating has excellent static antifouling performance. The antifouling coating has no pollution to the environment ecology, is green and environment-friendly, has strong practicability and has wide application prospect in the field of marine antifouling.

Inventors

  • SUN JIAWEN
  • DUAN JIZHOU
  • ZHU YUQING
  • ZHAI XIAOFAN
  • ZHAO XIA
  • HOU BAORONG

Assignees

  • 中国科学院海洋研究所

Dates

Publication Date
20260505
Application Date
20240521

Claims (7)

  1. 1. A surface sulfonated organic silicon hydrogel antifouling coating is characterized in that the coating is obtained by soaking an organic silicon hydrogel coating in a solution of an organic substance containing hydroxyl and sulfonic acid groups for surface sulfonation treatment, wherein the mass concentration of the organic substance containing hydroxyl and sulfonic acid groups in the solution of the organic substance containing hydroxyl and sulfonic acid groups is 0.01-0.1 g/mL; The organic silicon hydrogel coating is formed by polymerizing different functional monomers on a substrate through a one-pot method under the condition of a free radical initiator and a cross-linking agent, wherein the organic silicon hydrogel coating comprises the following components in percentage by mass: 10-30% of methacryloxypropyl mono-terminated polydimethylsiloxane; 20-40% of N-vinyl pyrrolidone; 10-30% of polyethylene glycol methyl ether methacrylate; 5-10% of butyl acrylate; 15-35% of silane coupling agent 0.1-0.5% Of free radical initiator; 0.2-2% of cross-linking agent; And (3) soaking the organic silicon hydrogel coating in the solution of excessive organic matters containing hydroxyl and sulfonic acid groups for 12-24 hours under the stirring condition, so that the organic matters containing hydroxyl and sulfonic acid groups are subjected to condensation reaction, and grafting the organic matters containing hydroxyl and sulfonic acid groups into a polymer network, thereby obtaining the surface sulfonated organic silicon hydrogel antifouling coating.
  2. 2. The surface sulfonated organosilicon hydrogel stain-proofing coating of claim 1, wherein said hydroxyl and sulfonic acid group-containing organic matter is one or more of isethionic acid, 3-hydroxy propane sulfonic acid, 4-hydroxy butane sulfonic acid, 3-hydroxy benzene sulfonic acid, 4-hydroxy benzene sulfonic acid.
  3. 3. The surface sulfonated silicone hydrogel stain resist coating of claim 2, wherein said methacryloxypropyl mono-terminated polydimethylsiloxane has a molecular weight of 1000 to 1200; the molecular weight of the polyethylene glycol methyl ether methacrylate is 300-1000.
  4. 4. The surface sulfonated silicone hydrogel stain repellent coating of claim 2, wherein said silane coupling agent is one of gamma- (methacryloxy) propyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane; the free radical initiator is one of 2,2 '-azobisisobutyronitrile and 1,1' -azobis (cyclohexane carbonitrile); The cross-linking agent is one or more of N, N-methylene bisacrylamide, ethylene glycol dimethacrylate and methyl vinyl acrylate.
  5. 5. A method for preparing a surface sulfonated silicone hydrogel antifouling coating according to claim 1, wherein the silicone hydrogel coating is soaked in a solution of excessive hydroxyl and sulfonic acid group-containing organic matters for 12-24 hours under stirring, so that condensation reaction is carried out on the hydroxyl and sulfonic acid group-containing organic matters, and the hydroxyl and sulfonic acid group-containing organic matters are grafted into a polymer network, thereby obtaining the surface sulfonated silicone hydrogel antifouling coating.
  6. 6. The method for preparing a surface sulfonated silicone hydrogel stain repellent coating according to claim 5, wherein said silicone hydrogel coating is prepared by uniformly stirring methacryloxypropyl mono-terminated polydimethylsiloxane, N-vinylpyrrolidone, polyethylene glycol methyl ether methacrylate, butyl acrylate, and a silane coupling agent in proportion at room temperature, sequentially adding a free radical initiator and a crosslinking agent, continuing stirring for 1h, coating the uniformly mixed solution on different substrates, and performing bulk polymerization and crosslinking curing at 80 ℃ for 12h, and then immersing the obtained silicone hydrogel coating in deionized water for 24h to remove unreacted monomers and swell to equilibrium.
  7. 7. The method of claim 1, wherein the surface sulfonated silicone hydrogel stain-proofing coating is applied as a stain-proofing coating in marine stain-proofing field.

Description

Surface sulfonated organosilicon hydrogel antifouling coating and preparation method thereof Technical Field The invention belongs to the field of marine antifouling, and in particular relates to a surface sulfonated organosilicon hydrogel antifouling coating and a preparation method thereof. Background The living beings in the marine environment are complex and various, the quantity is huge, and the surface of facilities and equipment which are immersed in the sea water for a long time, including ocean platforms, offshore drilling facilities, ships and the like, is easy to be attached by marine fouling organisms, so that the normal operation and even damage of the facilities and equipment are affected. Since 2008 international marine organization prohibits the use of toxic tributyltin self-polishing antifouling paint, the development of green environmental protection type marine antifouling paint technology has been gaining more and more attention. Hydrogels are used in many applications in marine antifouling coatings due to their highly hydrophilic polymer networks. The antifouling mechanism is mainly that a hydration layer formed on the surface of the hydrogel can confuse judgment of fouling organisms to influence adhesion. However, only partial fouling organisms can be inhibited by this single antifouling mechanism. The organosilicon material can effectively reduce the attachment of fouling organisms due to the characteristics of low surface energy, low elastic modulus, low surface roughness and the like, or is easy to desorb under the condition of high water flow speed even if attached. However, in an environment with low seawater flow rate, the surface of the coating cannot remove a mucus layer secreted by microorganisms such as bacteria or diatom, and the antifouling effect on the surface of the marine static facility is poor. Hempaguard X7 series of antifouling paint which is pushed out by the old man in Danish, sea and rainbow is characterized in that a hydrogel component, an organosilicon component and an insecticide are physically blended, the insecticide is slowly released on the surface of a coating, the coating has an excellent real sea antifouling effect based on the synergistic antifouling effect of various antifouling strategy combinations, and the dock repair interval of 90 months on the surface of a ship can be maintained. Microorganisms in seawater can generally adhere rapidly and tightly to the surface of positively charged materials under the action of electrostatic attraction. When the pH value of the external solution is larger than the isoelectric point of the microorganism, the microorganism such as bacteria is negatively charged, for example, the Zeta potential of pseudomonas fluorescens in single EPS colloid suspension with the pH value of 8 is-43.2 mV, and the Zeta potential of chlorella in water with the pH value of 7 is-30 mV, so that a negative surface based on the principle of homomorphism (negative) with marine organisms, namely 'homomorphism repulsion', can be constructed to be friendly to avoid microorganism attachment. Rosenhahn et al demonstrated that the amount of settlement and adhesion strength of ulva spores on the prepared negatively charged Polytetrafluoroethylene (PTFE) surface was significantly less than on neutral and positively charged PTFE surfaces. Terda et al found that E.coli had a 23-fold lower adhesion density on the modified negatively charged Polyethylene (PE) surface than on the positively charged PE surface, and that the positively charged material surface biofilm was dense, homogeneous, single structure, while the negatively charged material surface biofilm was sparse, diverse, mushroom-like structure. Disclosure of Invention Aiming at the problem of short antifouling period of the current environment-friendly marine antifouling coating, the invention provides a surface sulfonated organosilicon hydrogel antifouling coating and a preparation method thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: A surface sulfonated organic silicon hydrogel antifouling coating is obtained by immersing an organic silicon hydrogel coating in a solution of hydroxyl and sulfonic acid group-containing organic matters for surface sulfonation treatment, wherein the mass concentration of the hydroxyl and sulfonic acid group-containing organic matters in the solution of hydroxyl and sulfonic acid group-containing organic matters is 0.01-0.1 g/mL. The organic matter containing hydroxyl and sulfonic acid groups is one or more of isethionic acid, 3-hydroxy propane sulfonic acid, 4-hydroxy butane sulfonic acid, 3-hydroxy benzene sulfonic acid and 4-hydroxy benzene sulfonic acid. The organic silicon hydrogel coating is formed by polymerizing different functional monomers on a substrate through a one-pot method under the condition of a free radical initiator and a cross-linking agent, wherein the organic silicon hydrogel