Silver ion modified super-smooth fluorine-containing amphiphilic block polymer, preparation method thereof and coating

Abstract

The invention relates to the technical field of marine antifouling, in particular to a silver ion modified super-smooth fluorine-containing amphiphilic block polymer, a preparation method thereof and a coating. The silver ion modified super-smooth fluorine-containing amphiphilic block polymer is prepared by reacting raw materials including silver acetate and a super-smooth fluorine-containing amphiphilic block polymer; the super-lubricity fluorine-containing amphiphilic block polymer is prepared from the following raw material components in parts by weight: 50 to 200 parts of fluorine-containing amphiphilic block polymer, 0.1 to 1 part of wetting dispersant, 100 to 300 parts of alcohol organic solvent, 1 to 10 parts of lubricant, 1 to 5 parts of silane oligomer and 0.1 to 1 g of crosslinking aid, according to the invention, a triple synergistic effect system with super lubrication, low surface energy and strong sterilization can be formed, and formation of marine biofouling can be inhibited to a great extent.

Description

Technical Field

[0001] This application relates to the technical field of marine antifouling, and more specifically, to a silver ion-modified super-slippery fluorinated amphiphilic block polymer, a preparation method thereof, and a coating. Background Art

[0002] The ocean contains abundant new energy, biological, and mineral resources. In recent years, the focus of people's development activities has gradually shifted towards the ocean. For the current marine industry, the formation of biofouling is an inevitable problem. Marine biofouling is caused by the continuous settlement, attachment, and improper reproduction of microorganisms, plants, and animals in the ocean on the solid surface of underwater substrates, which has many adverse effects on maritime shipping and the development and utilization of marine resources, seriously affecting the normal operation of ships and underwater facilities. The deposition and growth of fouling organisms such as marine bacteria, algae, and shellfish on the ship surface will form a biofilm, resulting in a significant increase in the surface roughness of the hull. The increase in roughness will increase the frictional resistance suffered by the ship during navigation, which not only increases fuel consumption and harmful gas emissions but also reduces the ship's sailing speed and shortens the service life of the hull. Subsequent cleaning and maintenance require a large amount of human, material, and time costs, resulting in huge economic losses.

[0003] With the gradual increase in the global green safety standards for marine application materials, it is of great practical significance to develop new environmentally friendly antifouling alternative materials. A common measure for ship protection is to coat the surface and components of the ship with a coating, which can protect the hull and its components, reduce corrosion, and extend their service life. Among them, super-slippery antifouling coatings have received continuous attention from researchers due to their low surface energy, low Young's modulus, and dynamic lubricating surface.

[0004] Compared with traditional low-surface-energy coatings, super-slippery coatings can significantly prevent marine organisms from adhering by constructing a dynamic lubricating surface. However, relying solely on a single dynamic antifouling mode, the physical "anti-adhesion" effect is limited, and the static antifouling effect is insufficient, unable to meet the actual needs of marine antifouling. On the other hand, the lubricants infused in super-slippery coatings are usually non-polar liquids such as silicone oil, fluoroether, or liquid paraffin. Such substances do not have a bactericidal effect and are extremely easy to lose, which greatly limits their application in the actual ocean. Currently, bactericides are generally added to super-slippery coatings to improve the bactericidal and antifouling effects. However, the use of bactericides will cause bacteria to develop a certain degree of drug resistance, and the introduction of such materials cannot fundamentally avoid the attachment of biofilms. Therefore, achieving the efficient and long-term service of super-slippery coatings is the primary problem to be overcome at this stage.

[0005] Super-slippery coatings face problems such as easy loss of lubricants, overuse of fungicides, and easy accumulation of biofilms. How to better fix lubricants, reduce the use of fungicides, and solve the problem of biofilm accumulation remains the focus of current research. Patent CN115895310A discloses a bionic super-slippery long-lasting antifouling coating based on a micro-nano porous structure, its preparation method and application. However, this patented coating has problems such as a lack of effective antifouling agents and the inability to effectively avoid marine biofouling. Patent CN118852934A discloses a self-assembly system as the main body of the coating, with PAA and PAH layer-by-layer self-assembly as the substrate, and the design of micro-nano structures reduces the loss of lubricating oil. However, this patented coating has great limitations in use, requires prefabricating a coating on a metal sample, and the size and construction performance of the metal sample will be restricted, making it difficult to achieve in actual applications, etc. Summary of the Invention

[0006] The present application provides a silver ion-modified super-slippery fluorinated amphiphilic block polymer, its preparation method, and a coating. The lubricant, fluorinated amphiphilic block polymer, and silver ions are effectively combined to prepare an antifouling resin. Utilizing the characteristics of the fluorinated amphiphilic block polymer, the lubricant and silver ions are coated, thereby achieving the effect of reducing the loss of the lubricant and synergistic antifouling with silver nanoparticles. A triple synergistic action system of "super-lubrication, low surface energy, and strong bactericidal effect" can greatly inhibit the formation of marine biofouling.

[0007] In the first aspect, the present application provides a silver ion-modified super-slippery fluorinated amphiphilic block polymer, adopting the following technical solution:

[0008] A silver ion-modified super-slippery fluorinated amphiphilic block polymer, which is prepared by reacting silver acetate with a super-slippery fluorinated amphiphilic block polymer. The raw materials of the super-slippery fluorinated amphiphilic block polymer include the following components in parts by weight: 50 - 200 parts of fluorinated amphiphilic block polymer, 0.1 - 1 part of wetting and dispersing agent, 100 - 300 parts of alcohol organic solvent, 1 - 10 parts of lubricant, 1 - 5 parts of silane oligomer, 0.1 - 1 g of crosslinking aid;

[0009] The raw materials of the fluorinated amphiphilic block polymer include the following components in parts by weight: 5 - 30 parts of copper bromide, 5 - 30 parts of catalyst, 1000 - 5000 parts of alcohol organic solvent, 200 - 1000 parts of hydrophilic acrylate, 50 - 300 parts of ATRP polymerization initiator, 200 - 1000 parts of hydrophobic fluorinated acrylate.

[0010] By adopting the above technical solutions, the super-slippery fluorinated amphiphilic block polymer prepared in this application is synthesized by a controlled polymerization method from a hydrophilic material acrylate and a hydrophobic material fluorinated acrylate, and can freely change the ratio of the hydrophilic material to the hydrophobic material, and load the super-slippery material to the maximum extent. Through a hydrophobic modification method, a hydrophobic lubricant is coated on the surface of the polymer, and then a silane oligomer gel is coated on the surface of the hydrophobic lubricant to form a stable super-slippery fluorinated amphiphilic block polymer; such a material structure can effectively protect the lubricant substance, reduce the loss of the lubricant, and the hydrophobic lubricant does not affect its release during film formation on the basis of being stable in the aqueous phase. During the subsequent working process, the lubricant substance can also be stably released, playing a good physical "anti-adhesion" effect, and thus the use of fungicides can be relatively reduced.

[0011] Moreover, the block polymer prepared in this application can not only effectively protect the lubricant substance, but also, through the electrostatic and chelation effects between the negatively charged anionic group at the hydrophilic end and the positively charged silver ions in the amphiphilic block polymer, silver ions can be directionally induced and loaded on the polymer surface. Therefore, this application can effectively combine the lubricant, the fluorinated amphiphilic block polymer and silver ions to prepare an antifouling resin, and utilize the characteristics of the fluorinated amphiphilic block polymer to coat the lubricant and silver ions, thereby achieving the effects of reducing the loss of lubricating oil and synergistic antifouling with silver nanoparticles. A triple synergistic action system of "super lubrication, low surface energy, and strong sterilization" can be formed, which can greatly inhibit the formation of marine biofouling.

[0012] Further, the hydrophilic acrylate is one or more of methoxypolyethylene glycol acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate.

[0013] Further, the ATRP polymerization initiator is one or more of ethyl 2-bromoisobutyrate, ethyl 2-chloroisobutyrate, and methyl 2-bromoisobutyrate.

[0014] Further, the hydrophobic acrylate is one or more of perfluorodecyl acrylate, perfluoromethyl acrylate, perfluoroethyl acrylate, and perfluorohexylethyl methacrylate.

[0015] Further, the lubricant is one or more of polymethylhydrosiloxane and polydimethylsiloxane.

[0016] Further, the silane oligomer is at least one of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexaphenyldisiloxane, and octaphenylcyclotetrasiloxane.

[0017] Further, the crosslinking aid is glycidyl ether siloxane oligomer.

[0018] By adopting the above technical solutions, the crosslinking assistant acts as an interfacial coupling agent to improve the compatibility between silver ions and the organic matrix.

[0019] Further, the silver acetate is an aqueous solution of silver acetate with a concentration of 1 - 10 mmol·L -1 , and the weight ratio of the silver acetate aqueous solution to the super-slippery fluorinated amphiphilic block polymer is (200 - 500):(50 - 200).

[0020] In a second aspect, the present application provides a method for preparing a silver ion-modified super-slippery fluorinated amphiphilic block polymer, adopting the following technical solutions:

[0021] A method for preparing a silver ion-modified super-slippery fluorinated amphiphilic block polymer includes the following steps:

[0022] Preparing a fluorinated amphiphilic block polymer: Dissolve copper bromide and a catalyst in an alcoholic organic solvent, then successively add a hydrophilic acrylate and an ATRP polymerization initiator, react at room temperature for 2 - 8 h, then add a hydrophobic acrylate, and continue to react for 18 - 24 h. After that, dissolve the obtained product in distilled water and dialyze it to obtain the fluorinated amphiphilic block polymer;

[0023] Preparing a super-slippery fluorinated amphiphilic block polymer: Under room temperature conditions, take the above-mentioned fluorinated amphiphilic block polymer, a wetting and dispersing agent, and an alcoholic organic solvent to disperse and obtain a solution; then transfer the above solution to a reactor, adjust the rotation speed to 2000 - 5000 r / min, dropwise add a lubricant, and the dropping time is 10 - 20 min. After the dropping is completed, continue to react for 10 - 30 min while maintaining the rotation speed unchanged. Mix the silane oligomer and the crosslinking assistant evenly and then dropwise add them to the above reaction solution, with a dropping time of 5 - 20 min. After continuing to react for 10 - 20 min, reduce the speed to stop the reaction, and adjust the pH value to 6 - 9 to obtain the desired super-slippery fluorinated amphiphilic block polymer;

[0024] Take the super-slippery fluorinated amphiphilic block polymer and place it in the silver acetate aqueous solution, mix it at a rotation speed of 200 - 500 r / min for 1 - 5 h, and after the mixing is completed, let it stand to form a silver ion-modified super-slippery fluorinated amphiphilic block polymer.

[0025] In a third aspect, the present application provides a coating using the above silver ion-modified super-slippery fluorinated amphiphilic block polymer, adopting the following technical solutions:

[0026] A coating using the above super-slippery fluorinated amphiphilic block polymer, the raw materials include the following components by weight: 20 - 50 parts of silver ion-modified super-slippery fluorinated amphiphilic block polymer; 15 - 30 parts of antifouling agent; 10 - 20 parts of solid filler; 0.5 - 2 parts of functional assistant; 15 - 30 parts of organic solvent.

[0027] Further, the antifouling agent is one or more of cuprous oxide, zinc oxide, cuprous thiocyanate, copper powder, copper pyrithione, zinc pyrithione, zineb, bromopyronil, 4,5-dichloro-2-n-octyl-3-isothiazolinone, medetomidine.

[0028] By adopting the above technical solution, in the coating system of the present application, three bactericidal systems of a hydrophobic lubricant, silver ions and an antifouling agent are combined. The hydrophobic lubricant and silver ions provided by the super-slippery fluorinated amphiphilic block polymer form a triple synergistic action system of "super lubrication, low surface energy, and strong bactericidal effect", which can greatly inhibit the formation of marine biological fouling; moreover, due to the excellent effect of the super-slippery fluorinated amphiphilic block polymer, the use of the antifouling agent can be relatively reduced, the influence of the antifouling agent on the coating adhesion can be reduced, and the bactericidal and antifouling system of the present application is more environmentally friendly.

[0029] In summary, the present application has the following beneficial effects:

[0030] 1. The synthesis process of the fluorinated amphiphilic block polymer in the present application is simple. By designing a hydrophobic modification method, a hydrophobic lubricant such as polymethylhydrosiloxane or polydimethylsiloxane is coated on the surface of the polymer, and then the surface of the hydrophobic lubricant is coated with a silane oligomer gel, thereby reducing the loss of the lubricant; moreover, the hydrophobic lubricant does not affect its release during film formation on the basis of being stable in the aqueous phase.

[0031] 2. In the present application, due to the electrostatic and chelation effects between the negatively charged anionic group at the hydrophilic end of the fluorinated amphiphilic block polymer and the positively charged silver ions, the silver ions can be firmly bound in the polymer, so that the nano silver is not easily detached, thereby reducing the long-term antifouling problem during the application of nano silver.

[0032] 3. The coating formulation of the present application adds a small amount of antifouling agent as a bactericide. Based on the synergistic effect between silver ions and the bactericide, it is expected to better exert the real-time antifouling effect of the composite coating, effectively reduce the dosage of the bactericide, and the coating prepared by using this system is environmentally friendly and can be used as an effective strategy for marine antifouling.

[0033] 4. When the present application is actually applied to the field of marine antifouling, when the coating sample is hung in a standard sea area according to the standard requirements, the adhesion can reach level 0, the impact resistance is ≥50 cm, the immersion resistance is level 0, and the biological fouling area is all below 1%, showing very good long-term marine antifouling performance. Description of the Drawings

[0034] Figure 1 It is the plate culture result (Staphylococcus aureus) of the control group in Example 1.

[0035] Figure 2 It is the plate culture result (Escherichia coli) of the control group in Example 1.

[0036] Figure 3 It is a graph showing the test results of the anti - Staphylococcus aureus and Escherichia coli performance in the laboratory of Example 1. Specific embodiments

[0037] The following further elaborates on the present application in conjunction with the accompanying drawings and examples.

[0038] In the specific embodiments of the present application, unless otherwise specified, the raw material substances can be obtained commercially.

[0039] The embodiments of the present application provide a silver - ion - modified super - slippery fluorinated amphiphilic block polymer, which is prepared by reacting silver acetate with the super - slippery fluorinated amphiphilic block polymer; the raw materials of the super - slippery fluorinated amphiphilic block polymer by weight include the following components: 50 - 200 parts of fluorinated amphiphilic block polymer, 0.1 - 1 part of wetting and dispersing agent, 100 - 300 parts of alcohol organic solvent, 1 - 10 parts of lubricant, 1 - 5 parts of silane oligomer, 0.1 - 1 g of cross - linking aid;

[0040] The raw materials of the fluorinated amphiphilic block polymer by weight include the following components: 5 - 30 parts of copper bromide, 5 - 30 parts of catalyst, 1000 - 5000 parts of alcohol organic solvent, 200 - 1000 parts of hydrophilic acrylate, 50 - 300 parts of ATRP polymerization initiator, 200 - 1000 parts of hydrophobic fluorinated acrylate.

[0041] Furthermore, the wetting and dispersing agent is one or several of cationic wetting and dispersing agents, amphoteric wetting and dispersing agents, and electrically neutral wetting and dispersing agents. Further, it can be sodium dodecyl sulfate, sulfonates, polyoxyethylene ethers, quaternary ammonium salts, such as BYKUMEN, ANTI - TERRA - USG, ANTI - TERRA - U80, ANTI - TERRA - U, BYK - 346.

[0042] The alcohol organic solvent is one or several of isopropanol, isobutanol, ethanol, methanol, trifluoroethanol, ethylene glycol, n - butanol, butanol, propylene glycol, butanediol.

[0043] Furthermore, the hydrophilic acrylate is one or several of methoxypolyethylene glycol acrylate, 2 - hydroxyethyl acrylate, 2 - hydroxypropyl acrylate.

[0044] Furthermore, the ATRP polymerization initiator is one or several of ethyl 2 - bromoisobutyrate, ethyl 2 - chloro - 2 - methylpropionate, methyl 2 - bromoisobutyrate.

[0045] Further, the hydrophobic acrylate is one or more of perfluorodecyl acrylate, perfluoromethyl acrylate, perfluoroethyl acrylate, and perfluorohexylethyl methacrylate.

[0046] Further, the lubricant is one or more of polymethylhydrosiloxane and polydimethylsiloxane.

[0047] Further, the silane oligomer is at least one of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexaphenyldisiloxane, and octaphenylcyclotetrasiloxane.

[0048] Further, the crosslinking aid is glycidyl ether siloxane oligomer, and the manufacturer is Aladdin.

[0049] Further, the silver acetate is an aqueous solution of silver acetate at 1 - 10 mmol·L -1 and the weight ratio of the aqueous silver acetate solution to the super-slippery fluorinated amphiphilic block polymer is (200 - 500):(50 - 200).

[0050] This application also provides a preparation method of a silver ion-modified super-slippery fluorinated amphiphilic block polymer, including the following steps:

[0051] Prepare the fluorinated amphiphilic block polymer: Dissolve copper bromide and a catalyst in an alcoholic organic solvent, then sequentially add a hydrophilic acrylate and an ATRP polymerization initiator, react at room temperature for 2 - 8 h, then add a hydrophobic acrylate, and continue to react for 18 - 24 h. After that, dissolve the obtained product in distilled water and dialyze to obtain the fluorinated amphiphilic block polymer;

[0052] Prepare the super-slippery fluorinated amphiphilic block polymer: Under room temperature conditions, take the above-mentioned fluorinated amphiphilic block polymer, a wetting dispersant, and an alcoholic organic solvent to disperse and obtain a solution; then transfer the above solution to a reactor, adjust the rotation speed to 2000 - 5000 r / min, dropwise add the lubricant, and the dropping time is 10 - 20 min. After the dropping is completed, continue to react for 10 - 30 min while maintaining the rotation speed unchanged. Mix the silane oligomer and the crosslinking aid evenly and then dropwise add them to the above reaction solution. The dropping time is 5 - 20 min. After continuing to react for 10 - 20 min, reduce the speed to stop the reaction, and adjust the pH value to 6 - 9 to obtain the desired super-slippery fluorinated amphiphilic block polymer;

[0053] Take the super-slippery fluorinated amphiphilic block polymer and place it in the aqueous silver acetate solution, mix at a rotation speed of 200 - 500 r / min for 1 - 5 h, and after mixing, let it stand to form a silver ion-modified super-slippery fluorinated amphiphilic block polymer.

[0054] Specifically, a fluorinated amphiphilic block polymer is prepared as follows: 5 - 30 g of copper bromide and 5 - 30 g of the catalyst tris[2-(dimethylamino)ethyl]amine are successively added to 1 - 5 kg of an alcoholic organic solvent and ultrasonically dissolved for 20 - 60 min. Then, 200 - 1000 g of a hydrophilic acrylate and 50 - 300 g of an ATRP polymerization initiator are successively added. After reacting at room temperature for 2 - 8 h, 200 - 1000 g of a hydrophobic acrylate is added, and the reaction continues for 18 - 24 h. The resulting product is dissolved in distilled water and dialyzed for 48 h to obtain the fluorinated amphiphilic block polymer;

[0055] To prepare a super-slippery fluorinated amphiphilic block polymer: At room temperature, 50 - 200 g of the above-mentioned fluorinated amphiphilic block polymer, 0.1 - 1 g of a wetting and dispersing agent, and 100 - 300 g of an alcoholic organic solvent are placed in a rotary disk reactor for dispersion, with the rotation speed controlled at 500 - 1000 r / min and the dispersion time lasting for 5 - 15 min. Then, the above solution is transferred to the reactor, the rotation speed is adjusted to 2000 - 5000 r / min, 1 - 10 g of a lubricant is added dropwise over 10 - 20 min. After the addition is completed, the reaction continues for 10 - 30 min while maintaining the rotation speed. After mixing 1 - 5 g of a silane oligomer and 0.1 - 1 g of a crosslinking aid evenly, they are added dropwise to the above reaction solution over 5 - 20 min. After continuing the reaction for 10 - 20 min, the speed is reduced to stop the reaction. Then, the above solution is transferred to the rotary disk reactor, and 0.1 - 1 g of a pH regulator is added at a rotation speed of 200 - 500 r / min to adjust the pH value to 6 - 9, and the dispersion time lasts for 5 - 20 min to obtain the desired super-slippery fluorinated amphiphilic block polymer.

[0056] To prepare a super-slippery fluorinated amphiphilic block polymer with bactericidal function: 50 - 200 g of the above-mentioned super-slippery fluorinated amphiphilic block polymer is placed in 200 - 500 g of an aqueous silver acetate solution and mixed at a rotation speed of 200 - 500 r / min for 1 - 5 h. After mixing, it is left to stand at 50 °C - 80 °C for 20 min - 60 min. Ag⁺ is introduced into the super-slippery fluorinated amphiphilic block polymer to form a silver ion-modified super-slippery fluorinated amphiphilic block polymer.

[0057] This application also provides a coating, and the raw materials include the following components by weight: 20 - 50 parts of silver ion-modified super-slippery fluorinated amphiphilic block polymer; 15 - 30 parts of antifouling agent; 10 - 20 parts of solid filler; 0.1 - 2 parts of functional additive; 15 - 30 parts of organic solvent.

[0058] Further, the antifouling agent is one or more of cuprous oxide, zinc oxide, cuprous thiocyanate, copper powder, copper pyrithione, zinc pyrithione, zineb, bromo-pyrrole nitrile, 4,5-dichloro-2-n-octyl-3-isothiazolinone, medetomidine.

[0059] The solid filler is one or more of titanium dioxide, talcum powder, barium sulfate, heavy calcium carbonate, light calcium carbonate, mica powder, bentonite, and iron oxide red. The particle size of titanium dioxide is 2000 mesh, and the particle sizes of talcum powder, barium sulfate, heavy calcium carbonate, light calcium carbonate, mica powder, and iron oxide red are 1000 - 2000 mesh.

[0060] The functional additives are one or more of a wetting and dispersing agent and an antifoaming agent. The wetting and dispersing agent can be sodium dodecyl sulfate, sulfonates, polyoxyethylene ethers, quaternary ammonium salts, such as BYK UMEN, ANTI - TERRA - USG, ANTI - TERRA - U80, ANTI - TERRA - U, BYK - 346; the antifoaming agent can be silicone - based BYK - 1796, BYK - 1760, BYK - 1799, etc.

[0061] The organic solvent is one or more of benzene - based and alcohol - based solvents.

[0062] A preparation method of a super - slippery fluorinated amphiphilic block polymer coating for marine antifouling includes the following steps: sequentially put the silver - ion - modified super - slippery fluorinated amphiphilic block polymer, organic solvent, antifouling agent, solid filler, and functional additives into a clean reaction kettle, stir evenly for 2 - 5 h, and then filter to obtain a super - slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0063] The following is an explanation through specific examples.

[0064] Example 1

[0065] Sequentially add 10 g of copper bromide and 10 g of the catalyst tris[2 - (dimethylamino)ethyl]amine into 2 kg of isopropanol solvent, ultrasonically dissolve for 30 min, then sequentially add 500 g of polyethylene glycol monomethyl ether acrylate and 200 g of ethyl 2 - bromoisobutyrate, react at room temperature for 6 h, then add 500 g of perfluorodecyl acrylate, continue to react for 20 h, and then dissolve the obtained product in distilled water and dialyze for 48 h to obtain a fluorinated amphiphilic block polymer;

[0066] Further, under normal temperature conditions, 100 g of the fluorine-containing amphiphilic block polymer, 0.5 g of sodium dodecyl sulfate, and 200 g of isopropanol solvent were placed in a rotary disk reactor for dispersion, with the rotation speed controlled at 800 r / min and the dispersion time lasting for 10 min; then the above solution was transferred to a reaction kettle, the rotation speed was adjusted to 3000 r / min, 5 g of polydimethylsiloxane was added dropwise, the dropping time was 15 min, and after the dropping was completed, the reaction continued for 20 min while maintaining the rotation speed unchanged. After mixing 3 g of hexamethyldisiloxane and 0.5 g of glycidyl ether siloxane oligomer evenly, they were added dropwise to the above reaction solution, the dropping time was 10 min, and after continuing the reaction for 15 min, the speed was reduced to stop the reaction. Then the above solution was transferred to a rotary disk reactor, sodium hydroxide was added at a rotation speed of 400 r / min, the pH value was adjusted to 8, and after the dispersion time lasted for 15 min, the desired super-slippery fluorine-containing amphiphilic block polymer could be obtained;

[0067] Further, 100 g of the super-slippery fluorine-containing amphiphilic block polymer was placed in 300 g of an aqueous silver acetate solution, and they were mixed at a rotation speed of 300 r / min for 3 h. After the mixing was completed, they were left standing at 60 °C for 60 min to obtain a silver ion-modified super-slippery fluorine-containing amphiphilic block polymer;

[0068] 300 g of the silver ion-modified super-slippery fluorine-containing amphiphilic block polymer, 200 g of xylene, 100 g of n-butanol, 200 g of cuprous oxide, 30 g of zinc oxide, 20 g of zineb, 100 g of talc powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate, and 5 g of silicone defoamer BYK-1799 were sequentially put into a clean reaction kettle and stirred evenly at 2000 r / min. After 3 h, filtration was carried out to obtain a super-slippery fluorine-containing amphiphilic block polymer coating for marine antifouling.

[0069] Example 2

[0070] 5 g of copper bromide and 5 g of the catalyst tris[2-(dimethylamino)ethyl]amine were successively added to a mixed solvent of 500 g of isopropanol and 500 g of trifluoroethanol for ultrasonic dissolution for 50 min, and then 200 g of 2-hydroxyethyl acrylate and 50 g of ethyl 2-chloroisobutyrate were successively added. After reacting at normal temperature for 3 h, 200 g of perfluoromethyl acrylate was added, and after continuing the reaction for 18 h, the obtained product was dissolved in distilled water and dialyzed for 48 h to obtain a fluorine-containing amphiphilic block polymer;

[0071] Further, at room temperature, 50 g of the fluorinated amphiphilic block polymer, 1 g of sodium dodecyl sulfate and 300 g of isopropanol solvent are placed in a rotary disk reactor for dispersion, the rotation speed is controlled at 1000 r / min, and the dispersion time lasts for 15 min; then the above solution is transferred to a reaction kettle, the rotation speed is adjusted to 2000 r / min, 10 g of polymethylhydrogensiloxane is added dropwise, the dropping time is 20 min, and after the dropping is completed, the reaction continues for 30 min while maintaining the rotation speed unchanged. After mixing 5 g of hexamethyldisiloxane and 1 g of glycidyl ether siloxane oligomer evenly, they are added dropwise to the above reaction solution, the dropping time is 20 min, and after continuing the reaction for 20 min, the speed is reduced to stop the reaction. Then the above solution is transferred to a rotary disk reactor, sodium hydroxide is added at a rotation speed of 400 r / min, the pH value is adjusted to 8, and after the dispersion time lasts for 15 min, the desired super-slippery fluorinated amphiphilic block polymer can be obtained;

[0072] Further, 200 g of the super-slippery fluorinated amphiphilic block polymer is placed in 400 g of an aqueous silver acetate solution, and they are mixed at a rotation speed of 500 r / min for 4 h. After the mixing is completed, it is left standing at 50 °C for 30 min to obtain a silver ion-modified super-slippery fluorinated amphiphilic block polymer;

[0073] 200 g of the silver ion-modified super-slippery fluorinated amphiphilic block polymer, 100 g of xylene, 150 g of n-butanol, 220 g of cuprous oxide, 50 g of zinc oxide, 20 g of copper pyrithione, 10 g of 4,5-dichloro-2-n-octyl-3-isothiazolinone, 80 g of talc powder, 80 g of light calcium carbonate, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate and 5 g of silicone defoamer BYK-1799 are successively put into a clean reaction kettle and stirred evenly at 2500 r / min. After 2.5 h, filtration is carried out to obtain a super-slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0074] Example 3

[0075] 30 g of copper bromide and 20 g of the catalyst tris[2-(dimethylamino)ethyl]amine are successively added to a mixed solvent of 1000 g of ethanol and 2000 g of butanol and ultrasonically dissolved for 60 min. Then, 1000 g of hydroxypropyl acrylate and 300 g of methyl 2-bromoisobutyrate are successively added. After reacting at room temperature for 8 h, 1000 g of perfluoroethyl acrylate is added, and after continuing the reaction for 24 h, the obtained product is dissolved in distilled water and dialyzed for 48 h to obtain a fluorinated amphiphilic block polymer;

[0076] Further, under normal temperature conditions, 200 g of the fluorine-containing amphiphilic block polymer, 1 g of a polyoxyethylene ether dispersant, and 300 g of an ethanol solvent are placed in a rotary disk reactor for dispersion. The rotation speed is controlled at 1000 r / min, and the dispersion time lasts for 15 min. Then, the above solution is transferred to a reaction kettle, the rotation speed is adjusted to 4000 r / min, 10 g of polydimethylsiloxane is added dropwise, and the dropping time is 20 min. After the dropping is completed, the reaction continues for 30 min while maintaining the rotation speed unchanged. After mixing 5 g of hexamethyldisiloxane and 1 g of glycidyl ether siloxane oligomer evenly, they are added dropwise to the above reaction solution. The dropping time is 20 min. After continuing the reaction for 20 min, the speed is reduced to stop the reaction. Then, the above solution is transferred to a rotary disk reactor, and sodium hydroxide is added at a rotation speed of 400 r / min to adjust the pH value to 6. After the dispersion time lasts for 15 min, the desired super-slippery fluorine-containing amphiphilic block polymer can be obtained;

[0077] Further, 200 g of the super-slippery fluorine-containing amphiphilic block polymer is placed in 500 g of an aqueous silver acetate solution, and they are mixed at a rotation speed of 500 r / min for 5 h. After the mixing is completed, they are allowed to stand at 80 °C for 60 min to obtain a silver ion-modified super-slippery fluorine-containing amphiphilic block polymer;

[0078] 300 g of the silver ion-modified super-slippery fluorine-containing amphiphilic block polymer, 200 g of toluene, 80 g of butanol, 250 g of cuprous oxide, 50 g of zinc oxide, 50 g of barium sulfate, 27 g of mica powder, 8 g of bentonite, 25 g of iron oxide red, 12 g of sodium dodecyl sulfate, and 8 g of an organosilicon defoamer BYK-1760 are sequentially placed into a clean reaction kettle and stirred evenly at 2700 r / min. After 3 h, filtration is carried out to obtain a super-slippery fluorine-containing amphiphilic block polymer coating for marine antifouling.

[0079] Example 4

[0080] 15 g of copper bromide and 30 g of the catalyst tris[2-(dimethylamino)ethyl]amine are sequentially added to a mixed solvent of 2000 g of methanol and 3000 g of n-butanol and ultrasonically dissolved for 20 min. Then, 600 g of methoxypolyethylene glycol acrylate and 300 g of methyl 2-bromoisobutyrate are sequentially added. After reacting at normal temperature for 4 h, 700 g of perfluorohexylethyl methacrylate is added, and the reaction continues for 22 h. Then, the obtained product is dissolved in distilled water and dialyzed for 48 h to obtain a fluorine-containing amphiphilic block polymer;

[0081] Further, under normal temperature conditions, 150 g of the fluorine-containing amphiphilic block polymer, 0.8 g of the quaternary ammonium salt dispersant, and 100 g of the n-butanol solvent were placed in a rotary disk reactor for dispersion. The rotation speed was controlled at 600 r / min, and the dispersion time lasted for 8 min. Then, the above solution was transferred to a reaction kettle, the rotation speed was adjusted to 2500 r / min, 1 g of polydimethylsiloxane was added dropwise, and the dropping time was 12 min. After the dropping was completed, the reaction continued for 10 min while maintaining the rotation speed unchanged. After mixing 1 g of hexamethyldisiloxane and 0.1 g of glycidyl ether siloxane oligomer evenly, they were added dropwise to the above reaction solution, the dropping time was 12 min, and after continuing the reaction for 22 min, the speed was reduced to stop the reaction. Then, the above solution was transferred to a rotary disk reactor, sodium hydroxide was added at a rotation speed of 400 r / min, the pH value was adjusted to 7, and after the dispersion time lasted for 15 min, the desired super-slippery fluorine-containing amphiphilic block polymer could be obtained;

[0082] Further, 50 g of the super-slippery fluorine-containing amphiphilic block polymer was placed in 200 g of an aqueous silver acetate solution, and they were mixed at a rotation speed of 450 r / min for 2.7 h. After the mixing was completed, it was left standing at 55 °C for 25 min to obtain a silver ion-modified super-slippery fluorine-containing amphiphilic block polymer;

[0083] 260 g of the silver ion-modified super-slippery fluorine-containing amphiphilic block polymer, 300 g of xylene, 150 g of cuprous oxide, 20 g of zinc oxide, 100 g of copper powder, 10 g of midazolam, 40 g of titanium dioxide, 50 g of barium sulfate, 27 g of mica powder, 8 g of bentonite, 25 g of iron oxide red, 6 g of sulfonate dispersant, and 4 g of silicone defoamer BYK-1760 were sequentially placed into a clean reaction kettle and stirred evenly at 2200 r / min. After 5 h, filtration was carried out to obtain a super-slippery fluorine-containing amphiphilic block polymer coating for marine antifouling.

[0084] Example 5

[0085] 10 g of copper bromide and 15 g of the catalyst tris[2-(dimethylamino)ethyl]amine were sequentially added to 2000 g of trifluoroethanol solvent and ultrasonically dissolved for 30 min. Then, 500 g of polyethylene glycol monomethyl ether acrylate and 300 g of methyl 2-bromoisobutyrate were sequentially added. After reacting at room temperature for 4 h, 700 g of perfluorodecyl acrylate was added, and after continuing the reaction for 22 h, the obtained product was dissolved in distilled water and dialyzed for 48 h to obtain a fluorine-containing amphiphilic block polymer;

[0086] Further, at room temperature, 200 g of the fluorinated amphiphilic block polymer, 0.1 g of the sulfonate dispersant, and 280 g of the trifluoroethanol solvent are placed in a rotary disk reactor for dispersion, with the rotation speed controlled at 800 r / min and the dispersion time lasting for 12 min; then the above solution is transferred to a reaction kettle, the rotation speed is adjusted to 3500 r / min, 9 g of polydimethylsiloxane is added dropwise, the dropping time is 14 min, and after the dropping is completed, the reaction continues for 20 min while maintaining the rotation speed unchanged. After mixing 5 g of octamethylcyclotetrasiloxane and 1 g of glycidyl ether siloxane oligomer evenly, they are added dropwise to the above reaction solution, the dropping time is 15 min, and after continuing the reaction for 27 min, the speed is reduced to stop the reaction. Then the above solution is transferred to a rotary disk reactor, sodium hydroxide is added at a rotation speed of 400 r / min, the pH value is adjusted to 9, and after the dispersion time lasts for 15 min, the desired super-slippery fluorinated amphiphilic block polymer can be obtained;

[0087] Further, 160 g of the super-slippery fluorinated amphiphilic block polymer is placed in 360 g of an aqueous silver acetate solution, and they are mixed at a rotation speed of 250 r / min for 3 h. After the mixing is completed, it is left standing at 60 °C for 35 min to obtain a silver ion-modified super-slippery fluorinated amphiphilic block polymer;

[0088] 400 g of the silver ion-modified super-slippery fluorinated amphiphilic block polymer, 300 g of xylene, 200 g of cuprous oxide, 40 g of barium sulfate, 35 g of mica powder, 5 g of bentonite, 20 g of iron oxide red, 5 g of a polyoxyethylene ether dispersant, and 5 g of an organosilicon defoamer BYK-1760 are successively placed in a clean reaction kettle and stirred evenly at 2200 r / min. After 5 h, filtration is carried out to obtain a super-slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0089] Example 6

[0090] 30 g of copper bromide and 20 g of the catalyst tris[2-(dimethylamino)ethyl]amine are successively added to a mixed solvent of 1000 g of ethanol and 2000 g of butanol and ultrasonically dissolved for 60 min. Then, 800 g of hydroxypropyl acrylate and 300 g of 2-bromoisobutyric acid methyl ester are successively added. After reacting at room temperature for 8 h, 1000 g of perfluoroethyl acrylate is added, and after continuing the reaction for 24 h, the obtained product is dissolved in distilled water and dialyzed for 48 h to obtain a fluorinated amphiphilic block polymer;

[0091] Further, under normal temperature conditions, 200 g of the fluorinated amphiphilic block polymer, 0.9 g of the sulfonate dispersant, and 280 g of trifluoroethanol solvent are placed in a rotary disk reactor for dispersion, with the rotation speed controlled at 800 r / min and the dispersion time lasting for 12 min; then the above solution is transferred to a reaction kettle, the rotation speed is adjusted to 3500 r / min, 9 g of polydimethylsiloxane is added dropwise, the dropping time is 14 min, and after the dropping is completed, the reaction continues for 20 min while maintaining the rotation speed unchanged. After mixing 5 g of decamethylcyclopentasiloxane and 1 g of glycidyl ether siloxane oligomer evenly, they are added dropwise to the above reaction solution, the dropping time is 15 min, and after continuing the reaction for 27 min, the speed is reduced to stop the reaction. Then the above solution is transferred to a rotary disk reactor, sodium hydroxide is added at a rotation speed of 400 r / min, the pH value is adjusted to 8, and after the dispersion time lasts for 15 min, the desired super-slippery fluorinated amphiphilic block polymer can be obtained;

[0092] Further, 100 g of the super-slippery fluorinated amphiphilic block polymer is placed in 300 g of silver acetate aqueous solution, and they are mixed at a rotation speed of 300 r / min for 3 h. After the mixing is completed, it is left standing at 60 °C for 60 min to obtain the silver ion-modified super-slippery fluorinated amphiphilic block polymer;

[0093] 500 g of the silver ion-modified super-slippery fluorinated amphiphilic block polymer, 150 g of xylene, 100 g of cuprous oxide, 50 g of zinc oxide, 90 g of talcum powder, 25 g of mica powder, 5 g of bentonite, 20 g of iron oxide red, 5 g of quaternary ammonium salt dispersant, and 5 g of silicone defoamer BYK-1796 are sequentially placed into a clean reaction kettle, and they are stirred evenly at 3000 r / min. After 4 h, filtration is carried out to obtain a super-slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0094] Comparative Example

[0095] Comparative Example 1

[0096] Conventional epoxy antirust primer H06-1 purchased from Liaoning Supote Paint Co., Ltd.

[0097] Comparative Example 2

[0098] 300 g of acrylic resin, 200 g of xylene, 100 g of n-butanol, 100 g of polymethylhydrosiloxane, 130 g of cuprous oxide, 20 g of zinc oxide, 100 g of talcum powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate, and 5 g of silicone defoamer BYK-1796 are sequentially placed into a clean reaction kettle, and they are stirred evenly at 2000 r / min. After 3 h, filtration is carried out to obtain a conventional super-slippery antifouling coating.

[0099] Comparative Example 3

[0100] 10 g of copper bromide and 10 g of the catalyst tris[2-(dimethylamino)ethyl]amine were successively added to 2 kg of isopropanol solvent and sonicated for dissolution for 30 min. Then, 500 g of methoxypolyethylene glycol acrylate and 200 g of ethyl 2-bromoisobutyrate were successively added. After reacting at room temperature for 6 h, 500 g of perfluorodecyl acrylate was added, and after continuing to react for 20 h, the resulting product was dissolved in distilled water and dialyzed for 48 h to obtain a fluorinated amphiphilic block polymer;

[0101] 300 g of the fluorinated amphiphilic block polymer, 200 g of xylene, 100 g of n-butanol, 200 g of cuprous oxide, 30 g of zinc oxide, 20 g of zineb, 100 g of talc powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate, and 5 g of the silicone defoamer BYK-1796 were successively placed into a clean reaction kettle, stirred evenly at 2000 r / min, and filtered after 3 h to obtain a fluorinated amphiphilic block polymer coating for marine antifouling.

[0102] Comparative Example 4

[0103] 10 g of copper bromide and 10 g of the catalyst tris[2-(dimethylamino)ethyl]amine were successively added to 2 kg of isopropanol solvent and sonicated for dissolution for 30 min. Then, 500 g of methoxypolyethylene glycol acrylate and 200 g of ethyl 2-bromoisobutyrate were successively added. After reacting at room temperature for 6 h, 500 g of perfluorodecyl acrylate was added, and after continuing to react for 20 h, the resulting product was dissolved in distilled water and dialyzed for 48 h to obtain a fluorinated amphiphilic block polymer;

[0104] Furthermore, at room temperature, 100 g of the above-mentioned fluorinated amphiphilic block polymer, 0.5 g of sodium dodecyl sulfate, and 200 g of isopropanol solvent were placed in a rotary disk reactor for dispersion, with the rotation speed controlled at 800 r / min and the dispersion time lasting for 10 min; then the above solution was transferred to a reaction kettle, the rotation speed was adjusted to 3000 r / min, 5 g of polydimethylsiloxane was added dropwise, the dropping time was 15 min, and after the dropping was completed, the reaction continued for 20 min while maintaining the rotation speed. After mixing 3 g of hexamethyldisiloxane and 0.5 g of glycidyl ether siloxane oligomer evenly, they were added dropwise to the above reaction solution, the dropping time was 10 min, and after continuing to react for 15 min, the speed was reduced to stop the reaction. Then the above solution was transferred to a rotary disk reactor, and sodium hydroxide was added at a rotation speed of 400 r / min to adjust the pH value to 8, and after the dispersion time lasted for 15 min, the desired super-slippery fluorinated amphiphilic block polymer could be obtained;

[0105] Take 300 g of super-slippery fluorinated amphiphilic block polymer, 200 g of xylene, 100 g of n-butanol, 200 g of cuprous oxide, 30 g of zinc oxide, 20 g of zineb, 100 g of talcum powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate and 5 g of silicone defoamer BYK-1796 and put them into a clean reactor in sequence. Stir evenly at 2000 r / min. After 3 h, filter to obtain a super-slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0106] Comparative Example 5

[0107] Take 200 g of acrylic self-polishing resin, 200 g of xylene, 100 g of n-butanol, 400 g of cuprous oxide, 70 g of zinc oxide, 50 g of zineb, 100 g of talcum powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate and 5 g of silicone defoamer BYK-1796 and put them into a clean reactor in sequence. Stir evenly at 2000 r / min. After 3 h, filter to obtain a conventional self-polishing antifouling coating with a high dosage of antifouling agent.

[0108] Comparative Example 6

[0109] Add 10 g of copper bromide and 10 g of catalyst tris[2-(dimethylamino)ethyl]amine to 2 kg of isopropanol solvent in sequence and dissolve them by ultrasonic for 30 min. Then add 500 g of polyethylene glycol monomethyl ether acrylate and 200 g of 2-bromoisobutyric acid ethyl ester in sequence. React at room temperature for 6 h, then add 500 g of perfluorodecyl acrylate. After continuing to react for 20 h, dissolve the obtained product in distilled water and dialyze for 48 h to obtain a fluorinated amphiphilic block polymer.

[0110] Furthermore, at room temperature, take 100 g of the above-mentioned fluorinated amphiphilic block polymer, 0.5 g of sodium dodecyl sulfate and 200 g of isopropanol solvent and disperse them in a rotary disk reactor. Control the rotation speed at 800 r / min and the dispersion time for 10 min. Then transfer the above solution to a reactor, adjust the rotation speed to 3000 r / min, dropwise add 5 g of polydimethylsiloxane, and the dropping time is 15 min. After the dropping is completed, continue to react for 20 min while maintaining the rotation speed unchanged. Mix 0.5 g of hexamethyldisiloxane and 0.5 g of glycidyl ether siloxane oligomer evenly and then dropwise add them to the above reaction solution. The dropping time is 10 min. After continuing to react for 15 min, reduce the speed to stop the reaction. Then transfer the above solution to a rotary disk reactor, add sodium hydroxide at 400 r / min to adjust the pH value to 8, and disperse for 15 min to obtain a super-slippery fluorinated amphiphilic block polymer synthesized with too little dosage of silane oligomer as required.

[0111] Further, 100 g of the super-slippery fluorinated amphiphilic block polymer was placed in 300 g of an aqueous silver acetate solution, and the mixture was stirred at 300 r / min for 3 h. After the mixing was completed, the mixture was allowed to stand at 60 °C for 60 min to obtain a silver ion-modified super-slippery fluorinated amphiphilic block polymer synthesized with an insufficient amount of silane oligomer;

[0112] 300 g of the silver ion-modified super-slippery fluorinated amphiphilic block polymer synthesized with an insufficient amount of silane oligomer, 200 g of xylene, 100 g of n-butanol, 200 g of cuprous oxide, 30 g of zinc oxide, 20 g of zineb, 100 g of talc powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate, and 5 g of the silicone defoamer BYK-1796 were sequentially placed into a clean reaction kettle and stirred evenly at 2000 r / min. After 3 h, filtration was carried out to obtain a super-slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0113] Comparative Example 7

[0114] 10 g of copper bromide and 10 g of the catalyst tris[2-(dimethylamino)ethyl]amine were sequentially added to 2 kg of an isopropanol solvent and ultrasonically dissolved for 30 min. Then, 500 g of polyethylene glycol monomethyl ether acrylate and 200 g of ethyl 2-bromoisobutyrate were sequentially added. After reacting at room temperature for 6 h, 500 g of perfluorodecyl acrylate was added, and the reaction continued for 20 h. The resulting product was then dissolved in distilled water and dialyzed for 48 h to obtain a fluorinated amphiphilic block polymer;

[0115] Further, at room temperature, 100 g of the above-mentioned fluorinated amphiphilic block polymer, 0.5 g of sodium dodecyl sulfate, and 200 g of an isopropanol solvent were placed in a rotary disk reactor for dispersion, and the rotation speed was controlled at 800 r / min, and the dispersion time lasted for 10 min; then the above solution was transferred to a reaction kettle, the rotation speed was adjusted to 3000 r / min, and 5 g of polydimethylsiloxane was added dropwise, and the dropping time was 15 min. After the dropping was completed, the reaction continued for 20 min while maintaining the rotation speed unchanged. 15 g of hexamethyldisiloxane and 0.5 g of glycidyl ether siloxane oligomer were mixed evenly and then added dropwise to the above reaction solution, and the dropping time was 10 min. After continuing the reaction for 15 min, the speed was reduced to stop the reaction. Then the above solution was transferred to a rotary disk reactor, and sodium hydroxide was added at a rotation speed of 400 r / min to adjust the pH value to 8, and the dispersion time lasted for 15 min to obtain a super-slippery fluorinated amphiphilic block polymer synthesized with an excessive amount of silane oligomer as required;

[0116] Further, 100 g of the super-slippery fluorinated amphiphilic block polymer was placed in 300 g of an aqueous silver acetate solution, and the mixture was stirred at 300 r / min for 3 h. After mixing, it was allowed to stand at 60 °C for 60 min to obtain a silver ion-modified super-slippery fluorinated amphiphilic block polymer synthesized with an excessive amount of silane oligomer.

[0117] Take 300 g of the silver ion-modified super-slippery fluorinated amphiphilic block polymer synthesized with a small amount of silane oligomer, 200 g of xylene, 100 g of n-butanol, 200 g of cuprous oxide, 30 g of zinc oxide, 20 g of zineb, 100 g of talc powder, 10 g of bentonite, 30 g of iron oxide red, 5 g of sodium dodecyl sulfate, and 5 g of the silicone defoamer BYK-1796 and put them into a clean reaction kettle in sequence. Stir evenly at 2000 r / min. After 3 h, filter to obtain a super-slippery fluorinated amphiphilic block polymer coating for marine antifouling.

[0118] Performance testing

[0119] The super-slippery fluorinated amphiphilic block polymer coatings prepared in the examples and the coatings prepared in the comparative examples were subjected to performance testing. The specific test methods and standards are as follows:

[0120] Adhesion testing was carried out in accordance with GB / T9286-2021;

[0121] Impact resistance testing was carried out in accordance with the national standard GB / T1732-2020;

[0122] Immersion resistance testing: The super-slippery fluorinated amphiphilic block polymer coatings for marine antifouling prepared in the examples and the coatings prepared in the comparative examples were respectively coated on steel plates. After drying for 7 d, half of the sample plates were immersed in seawater and half were exposed to air. After soaking for 12 months, observe and evaluate the film cracking, bubbling, film rusting, appearance color change, etc. The evaluation criteria are: 0-5 levels, with 0 level being the best and 5 level being the worst;

[0123] Antifouling performance testing was carried out in accordance with GB / T5370-2007. The test location was Qingdao Port, Shandong. With a 12-month test cycle, observe the biological fouling area on the test panels.

[0124] An antibacterial experiment on Staphylococcus aureus and Escherichia coli was carried out on Example 1 in the laboratory, specifically cultured at (37±1) °C and relative humidity RH>90% for 24 h.

[0125] The performance test results of the examples and the comparative examples are shown in Table 1.

[0126] The test results of the antibacterial experiment on Staphylococcus aureus and Escherichia coli in the laboratory of Example 1 are shown in Table 2 and Figures 1 - 3 as shown.

[0127] Table 1 Performance test results of each example and comparative example

[0128] Adhesion / level Impact resistance / cm Soaking resistance / level Biofouling area / % Example 1 0 ≥50 0 0.76 Example 2 0 ≥50 0 0.82 Example 3 0 ≥50 0 0.65 Example 4 0 ≥50 0 0.72 Example 5 0 ≥50 0 0.56 Example 6 0 ≥50 0 0.88 Comparative Example 1 0 ≥50 0 97 Comparative Example 2 1 ≥40 1 39 Comparative Example 3 0 ≥50 0 68 Comparative Example 4 0 ≥50 0 17 Comparative Example 5 2 ≥50 0 14 Comparative Example 6 0 ≥50 0 41 Comparative Example 7 0 ≥50 0 16

[0129] Table 2 Performance test results of Example 1 against Staphylococcus aureus and Escherichia coli

[0130]

[0131]

[0132] As can be seen from Table 1, for the super-slippery fluorinated amphiphilic block polymer coatings prepared in Examples 1-6 of the present application, their adhesion can all reach Grade 0, impact resistance ≥ 50 cm, immersion resistance is Grade 0, and the biofouling area is all below 1%, showing very good long-term marine antifouling performance.

[0133] As can be seen from Table 2 and Figures 1 - 3 it can be known that the super-slippery fluorinated amphiphilic block polymer coating prepared in Example 1 showed very good results in the antibacterial experiment tests against Staphylococcus aureus and Escherichia coli in the laboratory. Within one day, it could effectively inhibit the two bacteria, making it difficult for the bacteria to adhere and survive on the coating surface, indicating the extremely strong bactericidal performance of the coating modified with silver ions.

[0134] Compared with Examples 1-6, Comparative Example 1 is a conventional marine anti-corrosion coating without adding lubricating oil and anti-fouling poison. It can be seen that its adhesion, impact resistance and immersion performance are very good, indicating that the mechanical and durability performance of the coating itself is good. However, its anti-fouling performance is very poor and has basically no effect on marine anti-fouling. This is because the coating does not contain any anti-fouling resin and anti-fouling poison and cannot restrict marine fouling organisms. In the entire experimental comparison group, its biological fouling area experiment performance is the worst, and the biological fouling area reaches 97% after 12 months; Comparative Example 2 is a conventional super-slippery anti-fouling coating. Because the conventional super-slippery anti-fouling coating contains a large amount of super-slippery materials, its adhesion, impact resistance and immersion performance are slightly worse than those of the examples. And from the results of the 12-month panel test, the biological fouling area is 39%, indicating insufficient anti-fouling performance. This shows that the conventional super-slippery coating only relies on a single dynamic anti-fouling mode, and the physical "anti-adhesion" effect is limited, and the static anti-fouling effect is insufficient, and it cannot meet the actual needs of marine anti-fouling; Comparative Example 3 is a fluorinated amphiphilic block copolymer coating without coating lubricating liquid and silver ion modification. Its adhesion, impact resistance and immersion performance are very good, indicating that the coating prepared by the fluorinated amphiphilic block copolymer can meet the application requirements in terms of mechanical properties. However, its marine anti-fouling performance is poor, and the biological fouling area reaches 68% after 12 months. The resin is not coated with super-slippery materials and silver ion modification, and it is difficult to meet the requirements of marine anti-fouling applications only by the low surface energy hydrophobic property of fluorine; Comparative Example 4 is a super-slippery fluorinated amphiphilic block copolymer coating without silver ion modification. Compared with the previous examples, only the resin is not modified with silver ions, and its adhesion, impact resistance and immersion performance are still very good. However, the lack of silver ions in the resin makes the marine anti-fouling performance slightly worse, and the biological fouling area reaches 17% after 12 months, far less than 1% of the examples. This shows the importance of the "super-lubrication, low surface energy, strong sterilization" triple synergistic anti-fouling coating, and none of the triple synergies can be lacking.

[0135] In Comparative Example 5, on the basis of the conventional anti-fouling coating, the dosage of the anti-fouling agent was increased. Although its biological fouling area decreased compared with Comparative Example 1, its adhesion deteriorated significantly; Comparative Example 6 used a silver ion-modified super-slippery fluorinated amphiphilic block copolymer synthesized with too little silane oligomer, and Comparative Example 7 used a silver ion-modified super-slippery fluorinated amphiphilic block copolymer synthesized with too much silane oligomer. Both of their adhesion, impact resistance and immersion performance are very good, indicating that the coating prepared by the fluorinated amphiphilic block copolymer can meet the application requirements in terms of mechanical properties. However, their marine anti-fouling performance is poor, and the biological fouling area reaches 43% and 16% after 12 months, indicating that only an appropriate dosage of silane oligomer can well modify the silver ion-modified super-slippery fluorinated amphiphilic block copolymer.

[0136] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A silver ion-modified super-slippery fluorinated amphiphilic block polymer, characterized in that, The silver ion-modified super-slippery fluorinated amphiphilic block polymer is prepared from raw materials including silver acetate and a super-slippery fluorinated amphiphilic block polymer. The raw materials of the super-slippery fluorinated amphiphilic block polymer include the following components by weight: 50-200 parts of a fluorinated amphiphilic block polymer, 0.1-1 part of a wetting dispersant, 100-300 parts of an alcohol organic solvent, 1-10 parts of a lubricant, 1-5 parts of a silane oligomer, and 0.1-1 g of a crosslinking aid; The raw materials of the fluorinated amphiphilic block polymer include the following components by weight: 5-30 parts of copper bromide, 5-30 parts of a catalyst, 1000-5000 parts of an alcohol organic solvent, 200-1000 parts of a hydrophilic acrylate, 50-300 parts of an ATRP polymerization initiator, and 200-1000 parts of a hydrophobic fluorinated acrylate.

2. The silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, wherein The hydrophilic acrylate is one or more of methoxypolyethylene glycol acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate.

3. A silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, characterized in that, The ATRP polymerization initiator is one or more of ethyl 2-bromoisobutyrate, ethyl 2-chloroisobutyrate, and methyl 2-bromoisobutyrate.

4. A silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, characterized in that, The hydrophobic acrylate is one or more of perfluorodecyl acrylate, perfluoromethyl acrylate, perfluoroethyl acrylate, and perfluorohexylethyl methacrylate.

5. A silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, characterized in that, The lubricant is one or more of polymethylhydrosiloxane and polydimethylsiloxane.

6. The silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, wherein The silane oligomer is at least one of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexaphenyldisiloxane, and octaphenylcyclotetrasiloxane.

7. A silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, characterized in that, The crosslinking aid is glycidyl ether siloxane oligomer.

8. The silver ion-modified super-slippery fluorinated amphiphilic block polymer according to claim 1, characterized in that The silver acetate is an aqueous silver acetate solution with a concentration of 1-10 mmol·L -1 , and the weight ratio of the aqueous silver acetate solution to the super-slippery fluorinated amphiphilic block polymer is (200-500):(50-200).

9. A preparation method of the silver ion-modified super-slippery fluorinated amphiphilic block polymer according to any one of claims 1-8, characterized in that, It includes the following steps: Preparing a fluorinated amphiphilic block polymer: Dissolve copper bromide and a catalyst in an alcohol organic solvent, then sequentially add a hydrophilic acrylate and an ATRP polymerization initiator. After reacting at room temperature for 2-8 h, add a hydrophobic fluorinated acrylate, and continue to react for 18-24 h. Then dissolve the obtained product in distilled water and dialyze to obtain a fluorinated amphiphilic block polymer; Preparing a super-slippery fluorinated amphiphilic block polymer: Under room temperature conditions, take the above-mentioned fluorinated amphiphilic block polymer, a wetting dispersant, and an alcohol organic solvent and disperse them to obtain a solution; then transfer the above solution to a reactor, adjust the rotation speed to 2000-5000 r / min, dropwise add a lubricant, and the dropping time is 10-20 min. After the dropping is completed, continue to react for 10-30 min while maintaining the rotation speed unchanged. Mix the silane oligomer and the crosslinking aid evenly and then dropwise add them to the above reaction solution, and the dropping time is 5-20 min. After continuing to react for 10-20 min, reduce the speed to stop the reaction, and adjust the pH value to 6-9 to obtain the desired super-slippery fluorinated amphiphilic block polymer; Take the super-slippery fluorinated amphiphilic block polymer and place it in an aqueous silver acetate solution, mix it at a rotation speed of 200-500 r / min for 1-5 h, and after the mixing is completed, let it stand to form a silver ion-modified super-slippery fluorinated amphiphilic block polymer.

10. A coating using the silver ion-modified super-slippery fluorinated amphiphilic block polymer according to any one of claims 1-8, characterized in that, The raw materials include the following components by weight: 20 - 50 parts of silver ion - modified super - slippery fluorinated amphiphilic block polymer; 15 - 30 parts of antifouling agent; 10 - 20 parts of solid filler; 0.5 - 2 parts of functional additive; 15 - 30 parts of organic solvent.

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