Preparation method of special high-adhesion antifouling paint for yachts

Abstract

The invention discloses a preparation method of a special high-adhesion antifouling paint for yachts. The preparation method comprises the following steps: preparing antifouling paint resin from catechol monomers containing unsaturated double bonds, acrylate monomers containing epoxy groups, silane acrylate monomers and acrylic monomers through atom transfer radical polymerization; and mixing the resin with the amino modified pigment, the antifouling agent and the like to obtain the antifouling paint. Compared with the traditional antifouling paint, the catechol structure contained in the antifouling paint can form strong interaction with various substrates, so that the adhesive force of the paint is greatly increased, and the yacht is prevented from falling off during high-speed sailing. The amino-modified pigment reacts with the epoxy group of the resin matrix, so that the pigment can be uniformly dispersed in the coating, the chromaticity deviation caused by deposition or falling of the pigment is avoided, and the yacht can keep the bright color of the coating for a long time. Amino and epoxy groups react to form a cross-linked structure, so that the hardness of the coating is increased, and the impact of water flow and silt in the yacht sailing process is resisted.

Description

Technical Field

[0001] The invention relates to an antifouling coating, in particular to a method for preparing a high-adhesion antifouling coating specially used for yachts. Background Art

[0002] As a part of the marine economy, the yacht economy has, to a certain extent, promoted the shipbuilding industry, coating industry and other industries from extensive, low-cost, low-level repetitive manufacturing to intensive and refined development. In addition, the development of the yacht economy can drive the development of the regional economy. However, while yachts are used as law enforcement boats, leisure boats, and transportation boats for marine activities, they are also troubled by marine fouling problems. The attachment of fouling organisms to the bottom of the boat will greatly reduce the speed and maneuverability of the yacht, increase fuel consumption, and seriously affect the stability and safety performance of the yacht.

[0003] In order to prevent the attachment of marine fouling organisms, people have developed a series of antifouling coatings for specific purposes, such as antifouling coatings for aquaculture cages and antifouling coatings for ships, according to the characteristics of the use environment of different ships or equipment. However, since the advent of organotin antifouling coatings in the 1970s, there has not been a special antifouling coating for yachts. Seongjun Bae of the Korea Institute of Marine Biodiversity imitated the microstructure of the lotus leaf surface and used trichloroperfluorooctylsilane and silica nanoparticles to prepare a superhydrophobic antifouling coating with a micro-nano secondary structure. The coating was tested in real sea on yachts in the waters of Tongyeong, South Korea. Compared with yachts without antifouling coatings, the surface of yachts coated with micro-nano structure superhydrophobic coatings had a significant reduction in tunicates and bryozoans. However, the coating has poor long-term effectiveness. After the yacht was tested in seawater for 5 months, the antifouling effect of the antifouling coating failed. Summary of the invention

[0004] In view of the polychromaticity of yachts and the requirement of high adhesion of coatings at high speeds, the present invention provides a method for preparing a high-adhesion antifouling coating for yachts. The present invention uses acrylic monomers containing catechol structures and epoxy group structures, acrylic silane ester monomers and acrylic monomers as reaction raw materials to synthesize antifouling coating resins, and then mixes the synthesized resin, pigments treated with aminosilane coupling agents, antifouling agents, etc. in a certain proportion to obtain high-adhesion antifouling coatings for yachts.

[0005] In order to achieve the above-mentioned object of the invention, the preparation method of the high-adhesion antifouling coating for yachts provided by the present invention comprises the following steps: (1) A catechol monomer containing an unsaturated double bond, an acrylate monomer containing an epoxy group, an acrylic silane ester monomer and an acrylic acid monomer are polymerized by atom transfer free radical polymerization under the catalysis of cuprous bromide to obtain product a, i.e., a special antifouling resin for yachts; (2) adding pigment powder and amino-containing silane coupling agent to ethanol, stirring and reacting at a temperature of 40-60° C. for 2-5 hours, separating solid and liquid after the reaction, washing the solid with acetone, and drying the solid at below 50° C. to constant weight after washing, and obtaining product b, i.e., amino-modified pigment after drying; the pigment powder is selected from inorganic pigment powder, such as iron oxide red, titanium dioxide, chrome yellow, iron blue, etc.; (3) Mix product a, product b, chlorinated paraffin, copper-free antifouling agent, talcum powder, titanium dioxide, barium sulfate, zinc oxide, anti-settling agent and solvent to form a mixed material; add grinding balls to the mixed material for stirring and grinding until the material particles in the mixed material are less than or equal to 50 μm; after stirring and grinding, separate the solid and liquid, and the obtained liquid product is a high-adhesion antifouling coating for yachts. The grinding balls can be glass microbeads, alumina grinding balls, zirconium oxide grinding balls or silicon nitride grinding balls.

[0006] The specific synthesis steps of the product a are as follows: xylene, cyclohexanone, isopropanol and bipyridine are placed in a reaction container, after the bipyridine is dissolved, cuprous bromide and 2-bromoisobutyryl bromide are added, vacuuming and nitrogen filling are performed cyclically to ensure that there is no oxygen in the reaction container; under the temperature of 75-95°C, a mixed monomer composed of a catechol monomer containing an unsaturated double bond, an acrylate monomer containing an epoxy group, an acrylic silane ester monomer and an acrylic monomer is injected into the reaction container for reaction for 6-12 hours, and after the reaction is completed, the mixture is cooled to 18-30°C, and then the reaction product is quickly poured into ethanol at -25°C to -50°C, and solid-liquid separation is performed after the white precipitate is fully precipitated, and the separated solid is dried at below 50°C to constant weight to obtain product a, i.e., a special antifouling resin for yachts. The meaning of cyclic vacuuming and nitrogen filling is: vacuuming the reaction container, then filling it with nitrogen, vacuuming again, and then filling it with nitrogen again, and the cycle is repeated until there is no oxygen in the reaction container.

[0007] The amino-containing silane coupling agent is selected from 3-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane.

[0008] The mass ratio of the amino-containing silane coupling agent to the pigment powder is 0.05-0.8:1-6.

[0009] The amounts of the components used in step (3) are as follows by weight: 10-18 parts of product a, 1-4 parts of product b, 2-6 parts of chlorinated paraffin, 5-20 parts of copper-free antifouling agent, 1-5 parts of talc, 1-8 parts of titanium dioxide, 1-6 parts of barium sulfate, 10-25 parts of zinc oxide, 2-10 parts of anti-settling agent, and 10-30 parts of solvent.

[0010] 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 monomer containing unsaturated double bonds, acrylic ester monomer containing epoxy groups, acrylic silane ester monomer and acrylic monomer in the mixed monomer is 1-35:5-25:15-45:1-15; the mass ratio of cuprous bromide, bipyridine and the mixed monomer is 1:2:600-1000.

[0011] The catechol monomer containing unsaturated double bonds is 4-allylcatechol; the acrylate monomer containing epoxy groups is glycidyl methacrylate, glycidyl acrylate or glycidyl neodecanoate; the acrylic silane ester monomer is vinyl trimethoxysilane, vinyl triethoxysilane or vinyl triisopropoxysilane; and the acrylic monomer is acrylic acid or methacrylic acid.

[0012] The copper-free antifouling agent is one of zinc pyrithione, bromopyrrole nitrile and 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one or a mixture of two or more of them in any mass ratio; the anti-settling agent is one of polyamide wax or organic bentonite or a mixture of the two in any mass ratio; and the solvent is one of xylene and propylene glycol methyl ether or a mixture of the two in any mass ratio.

[0013] Compared with the prior art, the present invention has the following advantages: 1. Traditional antifouling coatings generally rely on hydrogen bonds and intermolecular forces to achieve adhesion to substrates, while the coating resin matrix of the present invention introduces a catechol structure that allows barnacles to firmly adhere to any substrate. The catechol structure can form a strong interaction with various substrates through π-π stacking, metal complexation, covalent crosslinking, etc. in addition to hydrogen bonds, so that the coating matrix can be firmly attached to various substrates, greatly increasing the adhesion of the coating and ensuring that the antifouling coating does not fall off when impacted by waves during high-speed yacht driving; 2. The carboxyl group introduced into the resin matrix can enhance the wettability of the pigment, making the color of the yacht more vivid; 3. In conventional antifouling coatings, pigments are generally mixed in the coating by physical mixing, which results in uneven dispersion and pigment shedding. However, the epoxy groups introduced into the resin matrix of the present invention can not only assist in enhancing the adhesion of the coating, but also form covalent bonds with the modified amino groups on the surface of the pigment, so that the pigment can be evenly dispersed. The pigment forms a strong bond with the resin matrix through covalent bonds, thus avoiding color deviation caused by pigment deposition or shedding. 4. The amino groups on the surface of the pigment react with the epoxy groups in the resin matrix to form a cross-linked structure, which increases the hardness of the coating and can resist the impact of water flow and sediment during the yacht's voyage. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 The figures are actual sea performance test diagrams of the yacht-specific antifouling coatings of Examples 1 to 5 and the control coating; Figure 2 This is a test diagram of the actual ship performance of the yacht-specific antifouling coating of Example 4. DETAILED DESCRIPTION

[0015] The present invention is further described in detail below by way of examples, which are not intended to limit the scope of the present invention. Example 1

[0016] (1) Add 10 g xylene, 15 g cyclohexanone, 5 g isopropanol and 0.1 g ligand bipyridine (2,2-bpy) to a 250 mL three-necked flask. After the ligand is dissolved, add 0.05 g CuBr and 0.05 g initiator 2-bromoisobutyryl bromide (BiBB). Vacuum and nitrogen are cycled for 3 times to ensure that there is no oxygen in the three-necked flask. Weigh 1 g 4-allylcatechol, 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 the above mixed monomer solution and slowly inject it into the three-necked flask through the rubber stopper of the three-necked flask. After the injection is completed, seal the injection port with sealing silicone grease. The temperature was raised to 85°C, and after reacting for 10 hours, the heating was turned off, and the mixture was cooled to 18-30°C. The reaction product was then quickly poured into ethanol at -25°C, and the white flocculent precipitate was filtered after being fully precipitated. The filtered solid (precipitate) was dried at 45°C to constant weight to obtain product a, i.e., a special antifouling resin for yachts; (2) 2 g of red iron oxide and 0.1 g of 3-aminopropyltrimethoxysilane were added to a three-necked flask containing ethanol, and magnetic stirring was performed at 50°C for 3 hours. After the reaction was completed, the modified red iron oxide was obtained by vacuum filtration. The modified red iron oxide was washed with acetone for 3 times, and then dried in an oven at 50°C for 6 hours to obtain product b, i.e., amino-modified pigment. (3) 10 g of antifouling resin for yachts, 4 g of amino-modified pigment, 5 g of chlorinated paraffin, 10 g of zinc pyrithione, 10 g of bromopyrrole nitrile, 4 g of talc, 5 g of titanium dioxide, 3 g of barium sulfate, 25 g of zinc oxide, 2 g of polyamide wax, 2 g of organic bentonite, 12 g of xylene and 8 g of propylene glycol methyl ether are mixed to form a mixture; grinding balls are added to the mixture and the mixture is stirred and ground by a high-speed disperser until the material particles in the mixture are less than or equal to 50 μm; after the stirring and grinding is completed, the solid and liquid are separated, and the obtained liquid product is a high-adhesion antifouling coating for yachts. Example 2

[0017] (1) Step (1) of this example is substantially the same as step (1) of Example 1, except that: 4-allylcatechol is 12 g, glycidyl acrylate is 10 g, and vinyltriisopropoxysilane is 20 g; (2) Step (2) of this embodiment is the same as step (2) of embodiment 1; (3) Step (3) of this embodiment is substantially the same as step (3) of embodiment 1, except that the amount of the yacht-specific antifouling resin is 12 g and the amount of the amino-modified pigment is 2 g. Example 3

[0018] (1) Step (1) of this example is substantially the same as step (1) of Example 1, except that: 4-allylcatechol is 18 g, glycidyl acrylate is 15 g, vinyl triisopropoxysilane is 25 g, and acrylic acid is 8 g; (2) Step (2) of this embodiment is the same as step (2) of embodiment 1; (3) Step (3) of this embodiment is substantially the same as step (3) of embodiment 1, except that: the amount of the yacht-specific antifouling resin is 14 g, the amount of the amino-modified pigment is 2 g, and the amount of the chlorinated paraffin is 3 g. Example 4

[0019] (1) Step (1) of this embodiment is substantially the same as step (1) of embodiment 1, except that: 4-allylcatechol is 25 g, glycidyl acrylate is 20 g, vinyl triisopropoxysilane is 30 g, and acrylic acid is 10 g; (2) Step (2) of this embodiment is the same as step (2) of embodiment 1; (3) Step (3) of this embodiment is substantially the same as step (3) of embodiment 1, except that: the amount of the special antifouling resin for yachts is 16 g, the amount of the amino-modified pigment is 2 g, the amount of the chlorinated paraffin is 3 g, the amount of the zinc pyrithione is 11 g, and the amount of the bromopyrrolecarbonitrile is 11 g. Example 5

[0020] (1) Step (1) of this example is substantially the same as step (1) of Example 1, except that: 4-allylcatechol is 32 g, glycidyl acrylate is 25 g, vinyl triisopropoxysilane is 36 g, and acrylic acid is 12 g; (2) Step (2) of this embodiment is the same as step (2) of embodiment 1; (3) Step (3) of this embodiment is substantially the same as step (3) of embodiment 1, except that: the amount of the special antifouling resin for yachts is 18 g, the amount of the amino-modified pigment is 2 g, the amount of the chlorinated paraffin is 3 g, the amount of the zinc pyrithione is 12 g, and the amount of the bromopyrrolecarbonitrile is 12 g.

[0021] The high adhesion antifouling coatings for yachts prepared in Examples 1 to 5 and the commercially available acrylic silane self-polishing antifouling coatings as control samples were subjected to adhesion tests according to the international standard ISO 4624-2023. The test results are shown in the following table:

[0022] It can be seen from the test results that the adhesion of the coatings obtained in Examples 1-5 of the present invention is significantly better than that of the 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-allylcatechol, glycidyl acrylate, vinyl triisopropoxysilane and acrylic acid, and the adhesion of the coating also increases with the increase of the content of the yacht-specific antifouling resin.

[0023] The high adhesion antifouling coatings for yachts prepared in Examples 1 to 5 and the commercially available acrylic silane self-polishing antifouling coatings were used to make hanging boards according to the requirements of the international standard GB / T 5370-2007 to test the antifouling performance of the antifouling coatings in real sea. The test area was in the coastal area of ​​Weifang for 3 years. The test results are shown in the attached manual. Figure 1 .

[0024] It can be seen from the test results that after 3 years of actual sea testing, the surface of the acrylic silane self-polishing antifouling coating is full of barnacles, while the surface of the yacht-specific antifouling coating prepared in Examples 1 to 5 is smooth, without any fouling organisms attached, and has a good antifouling effect.

[0025] The antifouling paint for yachts prepared in Example 4 was applied to patrol boat No. 37511 at the Happy Sea Yacht Wharf in Weifang Binhai District. After one year of sailing, no hard-shelled organisms such as barnacles attached to the yacht as a whole, and no paint shedding occurred. See the attached manual for details. Figure 2 .

[0026] In step (1) of Examples 1-5 of the present invention, the epoxy group-containing acrylic ester monomer is selected from glycidyl acrylate, the acrylic silane ester monomer is selected from vinyl triisopropoxy silane, and the acrylic acid monomer is selected from acrylic acid to achieve the synthesis of the special antifouling resin for yachts. If glycidyl methacrylate or glycidyl neodecanoate is used instead of glycidyl acrylate, vinyl trimethoxysilane or vinyl triethoxysilane is used instead of vinyl triisopropoxy silane, and methacrylic acid is used instead of acrylic acid, the special antifouling resin for yachts can still be synthesized and the same technical effect can be achieved, which will not be described one by one by examples here.

[0027] In step (3) of Examples 1-5 of the present invention, the copper-free antifouling agent is a combination of zinc pyrithione and bromopyrrolecarbonitrile. If any one of zinc pyrithione, bromopyrrolecarbonitrile and 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one is selected to replace the combination of zinc pyrithione and bromopyrrolecarbonitrile in the example, the preparation of the antifouling coating can also be achieved, and the same technical effect can be achieved. If a combination of zinc pyrithione and 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one or a combination of bromopyrrolecarbonitrile and 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one is selected to replace the combination of zinc pyrithione and bromopyrrolecarbonitrile in the example, the preparation of the antifouling coating can also be achieved, and the same technical effect can be achieved. The examples will not be used one by one to illustrate this.

Claims

1. A method for preparing a high-adhesion antifouling coating for yachts, characterized in that: The method comprises the following steps: (1) A catechol monomer containing an unsaturated double bond, an acrylate monomer containing an epoxy group, an acrylic silane ester monomer and an acrylic acid monomer are polymerized by atom transfer free radical polymerization under the catalysis of cuprous bromide to obtain product a, i.e., a special antifouling resin for yachts; (2) Adding pigment powder and amino-containing silane coupling agent to ethanol, stirring and reacting at a temperature of 40-60°C for 2-5 hours, separating solid and liquid after the reaction, washing the solid with acetone, and drying the solid at below 50°C to constant weight after drying to obtain product b, i.e., amino-modified pigment; (3) Mixing product a, product b, chlorinated paraffin, copper-free antifouling agent, talcum powder, titanium dioxide, barium sulfate, zinc oxide, anti-settling agent and solvent to form a mixed material; adding grinding balls to the mixed material to stir and grind until the material particles in the mixed material are less than or equal to 50 μm; after the stirring and grinding is completed, the solid and liquid are separated, and the obtained liquid product is a high-adhesion antifouling coating for yachts.

2. The method for preparing the high-adhesion antifouling coating for yachts according to claim 1, characterized in that: The specific synthesis steps of the product a are as follows: xylene, cyclohexanone, isopropanol and bipyridine are placed in a reaction container, and after the bipyridine is dissolved, cuprous bromide and 2-bromoisobutyryl bromide are added, and vacuuming and nitrogen filling are cyclically performed to ensure that there is no oxygen in the reaction container; at a temperature of 75-95° C., a mixed monomer formed by mixing a catechol monomer containing an unsaturated double bond, an acrylate monomer containing an epoxy group, an acrylic silane ester monomer and an acrylic monomer is injected into the reaction container for reaction for 6-12 hours, and after the reaction is completed, the mixture is cooled to 18-30° C., and then the reaction product is quickly poured into ethanol at -25° C. to -50° C., and after the white precipitate is fully precipitated, solid-liquid separation is performed, and the separated solid matter is dried below 50° C. to constant weight to obtain the product a, i.e., the special antifouling resin for yachts.

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

6. The method for preparing the high-adhesion antifouling coating for yachts as claimed 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 monomer containing unsaturated double bonds, acrylic ester monomer containing epoxy groups, acrylic silane ester monomer and acrylic monomer in the mixed monomer is 1-35:5-25:15-45:1-15; the mass ratio of cuprous bromide, bipyridine and the mixed monomer is 1:2:600-1000.

7. The method for preparing the high-adhesion antifouling coating for yachts as claimed in claim 2, characterized in that: The catechol monomer containing unsaturated double bonds is 4-allylcatechol; the acrylate monomer containing epoxy groups is glycidyl methacrylate, glycidyl acrylate or glycidyl neodecanoate; the acrylic silane ester monomer is vinyl trimethoxysilane, vinyl triethoxysilane or vinyl triisopropoxysilane; and the acrylic monomer is acrylic acid or methacrylic acid.

8. The method for preparing the high-adhesion antifouling coating for yachts as claimed in claim 5, characterized in that: The copper-free antifouling agent is one of zinc pyrithione, bromopyrrole nitrile and 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one or a mixture of two or more of them in any mass ratio; the anti-settling agent is one of polyamide wax or organic bentonite or a mixture of the two in any mass ratio; and the solvent is one of xylene and propylene glycol methyl ether or a mixture of the two in any mass ratio.

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