Preparation method of yacht special high-adhesion anti-fouling paint

Abstract

The application discloses a preparation method of a yacht special high-adhesion anti-fouling paint, which comprises the following steps: preparing an anti-fouling paint resin by atom transfer radical polymerization of a catechol monomer containing an unsaturated double bond, an acrylic ester monomer containing an epoxy group, a silane acrylate monomer and an acrylic monomer, and mixing the resin with an amino-modified pigment, an anti-fouling agent and the like to obtain the anti-fouling paint. Compared with traditional anti-fouling paint, the catechol structure contained in the application can form a strong interaction with various substrates, greatly increasing the adhesion of the paint and avoiding the paint from falling off when the yacht is sailing at a high speed. The amino-modified pigment can be uniformly dispersed in the paint by reacting with the epoxy group of the resin matrix, avoiding the color deviation caused by pigment deposition or falling off, and enabling the yacht to keep a bright paint color for a long time. The amino group reacts with the epoxy group to form a cross-linking structure, increasing the hardness of the coating and resisting the impact of water flow and silt during the sailing of the yacht.

Description

Technical Field

[0001] This invention relates to an antifouling coating, specifically to a method for preparing a high-adhesion antifouling coating for yachts. Background Technology

[0002] As a component of the marine economy, the yacht economy, to a certain extent, promotes the development of industries such as shipbuilding and painting from extensive, low-cost, and low-level repetitive manufacturing towards intensive and refined production. Furthermore, the development of the yacht economy can drive regional economic growth. However, while yachts are used for law enforcement, recreational, and transportation activities in the ocean, they are plagued by marine pollution problems. The attachment of fouling organisms to the hull significantly reduces the speed and maneuverability of yachts, increases fuel consumption, and seriously affects their stability and safety performance.

[0003] To prevent the attachment of marine fouling organisms, antifouling coatings for specific purposes, such as those for aquaculture cages and ships, have been developed based on the characteristics of different vessels or equipment operating environments. However, since the advent of organotin antifouling coatings in the 1970s, there has been no antifouling coating specifically designed for yachts. Seongjun Bae of the Korea Marine Biodiversity Research Institute, mimicking the microstructure of lotus leaf surfaces, prepared a superhydrophobic antifouling coating with a micro / nano secondary structure using trichloroperfluorooctylsilane and silica nanoparticles. The coating underwent real-world sea trials on yachts in the Tongyeong region of South Korea. Compared to yachts without the antifouling coating, those with the micro / nano structured superhydrophobic coating showed a significant reduction in sea squirts and bryozoans. However, the coating's long-term effectiveness was poor; after five months of testing in seawater, the antifouling effect of the coating failed. Summary of the Invention

[0004] To address the requirements of multicolor properties in yachts and the need for high adhesion of coatings at high speeds, this invention provides a method for preparing a high-adhesion antifouling coating specifically for yachts. This invention uses acrylic monomers containing catechol and epoxy groups, silane acrylate monomers, and acrylic monomers as reactants to synthesize an antifouling coating resin. Then, the synthesized resin, pigments treated with aminosilane coupling agents, and antifouling agents are mixed in a specific ratio to obtain the high-adhesion antifouling coating specifically for yachts.

[0005] To achieve the above-mentioned objectives, the method for preparing a high-adhesion antifouling coating for yachts provided by this invention includes the following steps:

[0006] (1) Catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers and acrylic monomers are polymerized by atom transfer radical under the catalysis of cuprous bromide to obtain product a, namely yacht antifouling resin.

[0007] (2) Add pigment powder and amino-containing silane coupling agent to ethanol, stir and react at 40-60℃ for 2-5 hours. After the reaction is completed, separate solid and liquid, wash the solid with acetone, and dry the solid at below 50℃ to constant weight. After drying, product b, i.e. amino-modified pigment, is obtained. The pigment powder is selected from inorganic pigment powder, such as iron oxide red, titanium dioxide, chrome yellow, iron blue, etc.

[0008] (3) Mix product a, product b, chlorinated paraffin, copper-free antifouling agent, talc, titanium dioxide, barium sulfate, zinc oxide, antisettling agent, and solvent to form a mixture; add grinding balls to the mixture and stir and grind until the particle size of the mixture is less than or equal to 50 μm; after stirring and grinding, separate the solid and liquid, and the resulting liquid product is a high-adhesion antifouling coating for yachts. The grinding balls are glass microspheres, alumina grinding balls, zirconia grinding balls, or silicon nitride grinding balls, etc.

[0009] The specific synthesis steps of product a are as follows: Xylene, cyclohexanone, isopropanol, and bipyridine are placed in a reaction vessel. After the bipyridine dissolves, cuprous bromide and 2-bromoisobutyryl bromide are added. The reaction is cyclically evacuated and purged with nitrogen to ensure that no oxygen is present in the reaction vessel. At a temperature of 75-95℃, a mixture of catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers, and acrylic monomers is injected into the reaction vessel and reacted for 6-12 hours. After the reaction is complete, the mixture is cooled to 18-30℃, and then the reaction product is quickly poured into ethanol at -25℃ to -50℃. After a white precipitate is fully separated, solid-liquid separation is performed. The separated solid is dried to constant weight below 50℃ to obtain product a, i.e., yacht-specific antifouling resin. The cyclic evacuation and nitrogen purging means: evacuating the reaction vessel, then purging with nitrogen, then evacuating again, and then purging with nitrogen again, repeating this cycle until no oxygen is present in the reaction vessel.

[0010] The amino-containing silane coupling agent is selected from 3-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, or N-phenyl-3-aminopropyltrimethoxysilane.

[0011] The mass ratio of the amino-containing silane coupling agent to the pigment powder is 0.05-0.8:1-6.

[0012] The amounts of each component in step (3) by weight are as follows: product a 10-18 parts, product b 1-4 parts, chlorinated paraffin 2-6 parts, copper-free antifouling agent 5-20 parts, talc powder 1-5 parts, titanium dioxide 1-8 parts, barium sulfate 1-6 parts, zinc oxide 10-25 parts, antisettling agent 2-10 parts, and solvent 10-30 parts.

[0013] The mass ratio of xylene, cyclohexanone, isopropanol, and bipyridine is 6-12:10-15:1-8:0.02-0.12; the mass ratio of cuprous bromide and 2-bromoisobutyryl bromide is 0.01-0.06:0.01-0.09; the mass ratio of catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers, and acrylic monomers in the mixed monomers is 1-35:5-25:15-45:1-15; and the mass ratio of cuprous bromide, bipyridine, and the mixed monomers is 1:2:600-1000.

[0014] The catechol monomer containing unsaturated double bonds is 4-allyl catechol; the acrylate monomer containing epoxy groups is glycidyl methacrylate, glycidyl acrylate, or glycidyl neodecanoate; the silane acrylate monomer is vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltriisopropoxysilane; and the acrylic monomer is acrylic acid or methacrylic acid.

[0015] The copper-free antifouling agent is a mixture of one or more of zinc pyridinethione, bromopyrrolidone, and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one in any mass ratio; the antisettling agent is a mixture of one or two of polyamide wax or organobentonite in any mass ratio; and the solvent is a mixture of one or two of xylene and propylene glycol methyl ether in any mass ratio.

[0016] Compared with the prior art, the present invention has the following advantages:

[0017] 1. Traditional antifouling coatings generally rely on hydrogen bonds and intermolecular forces to achieve adhesion to the substrate. However, in this invention, the coating resin matrix introduces a catechol structure that allows barnacles to adhere firmly to any substrate. The catechol structure can form strong interactions with various substrates through π-π stacking, metal complexation, covalent cross-linking, and other methods besides hydrogen bonds. This allows the coating matrix to adhere firmly to various substrates, greatly increasing the adhesion of the coating and ensuring that the antifouling coating does not fall off when the yacht is subjected to the impact of waves during high-speed travel.

[0018] 2. The carboxyl groups introduced into the resin matrix can enhance the wettability of the pigment, making the colors of the yacht more vibrant;

[0019] 3. In traditional antifouling coatings, pigments are generally mixed and added to the coating through physical mixing, which results in uneven dispersion and pigment shedding. However, in this invention, the epoxy groups introduced into the resin matrix can not only help enhance the adhesion of the coating, but also form covalent bonds with the modified amino groups on the pigment surface, so that the pigment can be evenly dispersed. Furthermore, the pigment forms a strong bond with the resin matrix through covalent bonds, avoiding color deviation caused by pigment deposition or shedding.

[0020] 4. The reaction between the amino groups on the pigment surface and the epoxy groups in the resin matrix forms a cross-linked structure, which increases the hardness of the coating and can resist the impact of water flow and sediment during yacht navigation. Attached Figure Description

[0021] Figure 1 These are real-sea performance test diagrams of the yacht-specific antifouling coatings of Examples 1-5 and the control coating;

[0022] Figure 2 This is a real-ship performance test diagram of the yacht-specific antifouling coating of Example 4. Detailed Implementation

[0023] The present invention will be further described in detail below through embodiments, but this is not intended to limit the scope of the invention. Example 1

[0024] (1) Add 10 g xylene, 15 g cyclohexanone, 5 g isopropanol and 0.1 g bipyridine (2,2-bpy) to a 250 mL three-necked flask in sequence. After the complexing agent dissolves, add 0.05 g CuBr and 0.05 g 2-bromoisobutyryl bromide (BiBB) as the initiator. Vacuum and purge with nitrogen three times to ensure that there is no oxygen in the three-necked flask. Weigh 1 g 4-allyl catechol, 5 g glycidyl acrylate, 15 g vinyltriisopropoxysilane and 1 g acrylic acid and mix them to form a mixed monomer. Use a syringe to draw up the above mixed monomer solution and slowly inject it into the three-necked flask through the rubber stopper. After the injection is complete, seal the injection port with sealing silicone grease. Heat to 85℃ and react for 10 hours. Then turn off the heating and cool to 18-30℃. Then quickly pour the reaction product into ethanol at -25℃. After the white flocculent precipitate is fully separated, filter it. Dry the filtered solid (precipitate) at 45℃ to constant weight to obtain product a, which is the yacht-specific antifouling resin.

[0025] (2) 2 g of iron oxide red and 0.1 g of 3-aminopropyltrimethoxysilane were added to a three-necked flask containing ethanol and magnetically stirred at 50°C for 3 hours. After the reaction was completed, the modified iron oxide red was obtained by vacuum filtration. The modified iron oxide red was washed three times with acetone and then dried in an oven at 50°C for 6 hours to obtain product b, i.e., amino-modified pigment.

[0026] (3) Mix 10g of yacht-specific antifouling resin, 4g of amino-modified pigment, 5g of chlorinated paraffin, 10g of zinc pyridinethione, 10g of bromopyrrolidone, 4g of talc, 5g of titanium dioxide, 3g of barium sulfate, 25g of zinc oxide, 2g of polyamide wax, 2g of organobentonite, 12g of xylene, and 8g of propylene glycol methyl ether to form a mixture; add grinding balls to the mixture and stir and grind it using a high-speed disperser until the particle size of the mixture is less than or equal to 50 μm; after stirring and grinding, separate the solid and liquid components, and the resulting liquid product is a yacht-specific high-adhesion antifouling coating. Example 2

[0027] (1) The steps (1) of this embodiment are basically the same as those of Example 1, except that: 4-allyl catechol is 12g, glycidyl acrylate is 10g, and vinyltriisopropoxysilane is 20g.

[0028] (2) Step (2) of this embodiment is the same as step (2) of embodiment 1;

[0029] (3) The steps (3) of this embodiment are basically the same as those of the steps (3) of embodiment 1, except that: the yacht-specific antifouling resin is 12g and the amino-modified pigment is 2g. Example 3

[0030] (1) The steps (1) of this embodiment are basically the same as those of Example 1, except that: 4-allyl catechol is 18g, glycidyl acrylate is 15g, vinyltriisopropoxysilane is 25g, and acrylic acid is 8g.

[0031] (2) Step (2) of this embodiment is the same as step (2) of embodiment 1;

[0032] (3) The steps (3) of this embodiment are basically the same as those of the steps (3) of embodiment 1, except that: the yacht-specific antifouling resin is 14g, the amino-modified pigment is 2g, and the chlorinated paraffin is 3g. Example 4

[0033] (1) The steps (1) of this embodiment are basically the same as those of Example 1, except that: 4-allyl catechol is 25g, glycidyl acrylate is 20g, vinyltriisopropoxysilane is 30g, and acrylic acid is 10g.

[0034] (2) Step (2) of this embodiment is the same as step (2) of embodiment 1;

[0035] (3) The steps (3) of this embodiment are basically the same as those of the steps (3) of embodiment 1, except that: the yacht-specific antifouling resin is 16g, the amino-modified pigment is 2g, the chlorinated paraffin is 3g, the zinc pyridinethione is 11g, and the bromopyrrolidinone is 11g. Example 5

[0036] (1) The steps (1) of this embodiment are basically the same as those of Example 1, except that: 4-allyl catechol is 32g, glycidyl acrylate is 25g, vinyltriisopropoxysilane is 36g, and acrylic acid is 12g.

[0037] (2) Step (2) of this embodiment is the same as step (2) of embodiment 1;

[0038] (3) The steps (3) of this embodiment are basically the same as those of the steps (3) of embodiment 1, except that: the yacht-specific antifouling resin is 18g, the amino-modified pigment is 2g, the chlorinated paraffin is 3g, the zinc pyridinethione is 12g, and the bromopyrrolidinone is 12g.

[0039] The yacht-specific high-adhesion antifouling coatings prepared in Examples 1 to 5 and a commercially available acrylic silane self-polishing antifouling coating used as a control sample were subjected to adhesion tests according to the international standard ISO 4624-2023. The test results are shown in the table below:

[0040]

[0041] The test results show that the adhesion of the coatings obtained in Examples 1-5 of this invention is significantly better than that of commercially available acrylic silane self-polishing antifouling coatings. The adhesion of the yacht-specific antifouling resin increases with the increase of the content of 4-allyl catechol, glycidyl acrylate, vinyltriisopropoxysilane, and acrylic acid, and the adhesion of the coating also increases with the increase of the content of the yacht-specific antifouling resin.

[0042] The yacht-specific high-adhesion antifouling coatings prepared in Examples 1 to 5, as well as commercially available acrylic silane self-polishing antifouling coatings, were used to conduct real-sea antifouling performance tests on panels according to the requirements of international standard GB / T 5370-2007. The test area was the sea area of ​​Weifang Binhai District, and the test period was 3 years. The test results are shown in the appendix of the instruction manual. Figure 1 .

[0043] The test results show that after three years of real-sea testing, the surface of the acrylic silane self-polishing antifouling coating was covered with barnacles, while the yacht-specific antifouling coatings prepared in Examples 1-5 had smooth surfaces without any fouling organisms, demonstrating good antifouling performance.

[0044] The antifouling coating for yachts prepared in Example 4 was applied to patrol boat No. 37511 at the Huanlehai Yacht Marina in Weifang Binhai District. After one year of sailing, the yacht showed no signs of barnacles or other hard-shelled organisms attaching to it, and the coating did not peel off. (See the attached instruction manual.) Figure 2 .

[0045] In step (1) of Examples 1-5 of this invention, the acrylate monomer containing epoxy groups is glycidyl acrylate, the silane acrylate monomer is vinyltriisopropoxysilane, and the acrylic monomer is acrylic acid to achieve the synthesis of yacht-specific antifouling resin. If glycidyl methacrylate or glycidyl neodecanoate is used instead of glycidyl acrylate, vinyltrimethoxysilane or vinyltriethoxysilane is used instead of vinyltriisopropoxysilane, and methacrylic acid is used instead of acrylic acid, the synthesis of yacht-specific antifouling resin can still be achieved and the same technical effect can be obtained. These will not be described in detail here with examples.

[0046] In step (3) of Examples 1-5 of this invention, the copper-free antifouling agent is a combination of zinc pyrithione and bromopyrrolidone. If any one of zinc pyrithione, bromopyrrolidone, and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is used to replace the combination of zinc pyrithione and bromopyrrolidone in the examples, the antifouling coating can also be prepared and the same technical effect can be achieved. If a combination of zinc pyrithione and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one or a combination of bromopyrrolidone and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is used to replace the combination of zinc pyrithione and bromopyrrolidone in the examples, the antifouling coating can also be prepared and the same technical effect can be achieved. The examples will not be used to illustrate these points one by one.

Claims

1. A method for preparing a high-adhesion antifouling coating specifically for yachts, characterized in that: The method includes the following steps: (1) Catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers and acrylic monomers are polymerized by atom transfer radical under the catalysis of cuprous bromide to obtain product a, namely yacht antifouling resin. (2) Add pigment powder and amino-containing silane coupling agent to ethanol, stir and react at 40-60℃ for 2-5 hours. After the reaction is completed, separate solid and liquid, wash the solid with acetone, and dry the solid at 50℃ to constant weight. After drying, product b, i.e. amino-modified pigment, is obtained. (3) Mix product a, product b, chlorinated paraffin, copper-free antifouling agent, talc, titanium dioxide, barium sulfate, zinc oxide, antisettling agent and solvent to form a mixture; add grinding balls to the mixture and stir and grind until the material particles in the mixture are less than or equal to 50 μm; after stirring and grinding, separate the solid and liquid, and the resulting liquid product is a high-adhesion antifouling coating for yachts.

2. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 1, characterized in that: The specific synthesis steps of product a are as follows: xylene, cyclohexanone, isopropanol, and bipyridine are placed in a reaction vessel. After the bipyridine dissolves, cuprous bromide and 2-bromoisobutyryl bromide are added. The reaction vessel is evacuated and purged with nitrogen to ensure that there is no oxygen in the reaction vessel. At a temperature of 75-95℃, a mixture of catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers, and acrylic monomers is injected into the reaction vessel and reacted for 6-12 hours. After the reaction is completed, the mixture is cooled to 18-30℃, and then the reaction product is quickly poured into ethanol at -25℃ to -50℃. After the white precipitate is fully separated, solid-liquid separation is performed. The separated solid is dried to constant weight below 50℃ to obtain product a, which is the yacht-specific antifouling resin.

3. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 1, characterized in that: The amino-containing silane coupling agent is selected from 3-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, or N-phenyl-3-aminopropyltrimethoxysilane.

4. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 1, characterized in that: The mass ratio of the amino-containing silane coupling agent to the pigment powder is 0.05-0.8:1-6.

5. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 1, characterized in that: The amounts of each component in step (3) by weight are as follows: product a 10-18 parts, product b 1-4 parts, chlorinated paraffin 2-6 parts, copper-free antifouling agent 5-20 parts, talc powder 1-5 parts, titanium dioxide 1-8 parts, barium sulfate 1-6 parts, zinc oxide 10-25 parts, antisettling agent 2-10 parts, and solvent 10-30 parts.

6. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 2, characterized in that: The mass ratio of xylene, cyclohexanone, isopropanol, and bipyridine is 6-12:10-15:1-8:0.02-0.12; the mass ratio of cuprous bromide and 2-bromoisobutyryl bromide is 0.01-0.06:0.01-0.09; the mass ratio of catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers, and acrylic monomers in the mixed monomers is 1-35:5-25:15-45:1-15; and the mass ratio of cuprous bromide, bipyridine, and the mixed monomers is 1:2:600-1000.

7. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 2, characterized in that: The catechol monomer containing unsaturated double bonds is 4-allyl catechol; the acrylate monomer containing epoxy groups is glycidyl methacrylate, glycidyl acrylate, or glycidyl neodecanoate; the acrylic monomer is acrylic acid or methacrylic acid.

8. The method for preparing the yacht-specific high-adhesion antifouling coating as described in claim 5, characterized in that: The copper-free antifouling agent is a mixture of one or more of zinc pyridinethione, bromopyrrolidone, and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one in any mass ratio; the antisettling agent is a mixture of one or two of polyamide wax or organobentonite in any mass ratio; and the solvent is a mixture of one or two of xylene and propylene glycol methyl ether in any mass ratio.

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