Marine organism-preventing drag-reducing paint for ships and preparation method of marine organism-preventing drag-reducing paint
By dividing ship anti-sea biodrag reduction paint into components A and B, and using hydrophobic glass fibers, acetone silver and hydrophobic nanosilicon dioxide to form a multi-layer hierarchical structure, the existing coating's pollution resistance is reduced and the toxicity of copper-based chemicals to the marine ecology is solved, significant drag reduction and pollution reduction effects are achieved, and the service life of the coating is extended.
Patent Information
- Application Number
- CN202411898751.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-23
- Publication Date
- 2025-04-15
AI Technical Summary
The existing ship coatings have reduced their pollution prevention capabilities year by year during the overhaul period, resulting in an increase in water resistance and copper-based chemicals have toxic effects on marine ecology.
The marine anti-sea bio-reduction paint is used, which is made of a mixture of components A and components B, where components A include hydrophobic glass fibers and copper acetone, and components B include hydrophobic nanosilicon dioxide and polypropylene resin. A multi-layer hierarchical structure is formed through mechanical locking and chemical bonding to enhance hydrophobic properties and mechanical strength.
It significantly improves the drag reduction effect and anti-fouling performance of the ship in water, extends the effective and continuous protection time of the coating to 5 to 8 years, reduces the adhesion of dirt and marine organisms, and reduces electrochemical corrosion and friction resistance.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of coatings, in particular to a ship anti-marine organism drag-reducing paint and a preparation method thereof. Background Art
[0002] Ships operate in the vast ocean, and their hulls are troubled by the attachment of marine organisms, which not only affects the energy consumption of ships, but also increases the operating costs of ships. In order to prevent the attachment and derivation of marine organisms, coatings containing copper-based chemicals are usually used. These chemicals can be slowly released into the water to prevent the attachment of marine organisms such as barnacles and seaweed. However, copper-based chemicals are toxic to the marine ecology. Long-term use will accumulate in the marine environment and affect marine organisms. Therefore, Wuxi self-polishing coatings are widely used in the market, including hydrolyzable and ordinary Wuxi self-polishing antifouling paints. Compared with traditional copper-based coatings, Wuxi self-polishing coatings contain less copper and have relatively less pollution to the environment. Its main principle is to release chemicals to inhibit or prevent marine organisms from attaching to the hull, and to slowly decompose and fall off the coating through water flushing. These chemicals usually have anti-biological activity, which can attract and lock microorganisms, thereby preventing them from growing on the hull and preventing the hull from being attached by organisms such as barnacles and mussels. However, the disadvantage of this coating is that during the 2-5 year overhaul period of a ship, as the coating peels off and falls off, the anti-fouling ability decreases year by year, and the hull's water resistance increases year by year. Summary of the invention
[0003] The object of the present invention is to provide a ship anti-marine organism drag-reducing paint and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.
[0004] To achieve the above object, the present invention provides the following technical solution: a ship anti-marine biological drag-reducing paint, which is prepared by mixing component A and component B in a mass ratio of 1 to 1.5:1;
[0005] Wherein, component A comprises material 1 and material 2 mixed in a mass ratio of 1:1.5-2, material 1 comprises the following components by mass: 20-40 parts of hydrophobic glass fiber, 30-50 parts of xylene, and 10-20 parts of acetone copper, and material 2 comprises the following components by mass: 40-60 parts of acrylic resin, 5-10 parts of n-butanol, and 1-5 parts of ethylbenzene;
[0006] Component B includes the following components by weight: 30-45 parts of polypropylene resin, 15-25 parts of filler, 15-25 parts of coloring pigment, 2-5 parts of hydrophobic nano-silicon dioxide, 10-20 parts of toluene, and 5-15 parts of additives.
[0007] Furthermore, the coloring pigment includes one or more of titanium dioxide, titanium dioxide, chromium oxide, iron oxide, lemon yellow, carbon black, toluidine red, barium sulfate, and talc.
[0008] Furthermore, the filler includes salts of barium, calcium, magnesium or aluminum, oxides of silicon or aluminum, or composite salts derived from salts and oxides.
[0009] Furthermore, the auxiliary agent includes one or more of an antioxidant, a promoter, a surfactant, a leveling agent, a defoaming agent, and an emulsifier.
[0010] A method for preparing a ship anti-marine organism drag-reducing paint, the method comprising the following steps:
[0011] S1: prepare 20-40 parts of hydrophobic glass fiber, 30-50 parts of xylene, 10-20 parts of acetone copper, prepare 40-60 parts of acrylic resin, 5-10 parts of n-butanol, and 1-5 parts of ethylbenzene, first add material 2 into a mixing device, then gradually add material 1 into the melted material 2, and mix. After completion, cool the mixture to room temperature or an appropriate temperature, add n-butanol solvent to dilute, filter, obtain a paint, and disperse the paint through a sand mill;
[0012] S2: preparing 30-45 parts of polypropylene resin, 15-25 parts of filler, 15-25 parts of coloring pigment, and 2-5 parts of hydrophobic nano-silicon dioxide for grinding, adding 10-20 parts of toluene and 5-15 parts of additives, coloring paint, obtaining color paste, and dispersing the color paste through a sand mill;
[0013] S3: input the treated color paste into a paint mixing tank, adjust it to a preset color, add the paint in step S1, and add the solvent and stir to obtain a ship anti-marine growth drag reduction paint.
[0014] Furthermore, in step S2, the hydrophobic nano-silicon dioxide is pre-mixed with a small amount of polypropylene resin, and then added to the remaining polypropylene resin, filler and coloring pigment for grinding.
[0015] Furthermore, the preparation method of the hydrophobic nano-silica comprises:
[0016] The silicon dioxide is dried at a certain temperature to remove moisture, and the dried silicon dioxide particles are placed in a plasma reactor, and a gas with active groups is introduced, and the gas is excited by a high-frequency electric field to generate plasma. Under the action of the plasma, the gas molecules are decomposed and react with the silicon dioxide surface to introduce active groups. After the reaction is completed, the silicon dioxide treated with plasma is obtained by cooling and collecting;
[0017] Dissolving an appropriate amount of hydrophobic molecules in an appropriate solvent to form a solution having a molar concentration of 0.1-1%;
[0018] The plasma-treated silica particles are immersed in a hydrophobic molecule solution for 12 to 24 hours. During the immersion process, the hydrophobic molecules react with the active groups on the surface of the silica to self-assemble into a hydrophobic monolayer film.
[0019] After the reaction is completed, the silica particles are taken out from the solution, washed with a solvent to remove unreacted hydrophobic molecules, and dried in a vacuum or drying oven at 60-80° C. to obtain hydrophobized silica.
[0020] Furthermore, the hydrophobic glass fiber is made by copolymerizing pyrophyllite, quartz sand, limestone, dolomite, colemanite, magnesite, dichlorosilane and trichlorosilane, comprising the following steps:
[0021] Dissolve dichlorosilane and trichlorosilane in an appropriate amount of solvent, add deionized water for hydrolysis reaction, react at 40-60°C for 1-3 hours to generate silanol groups, and after the reaction is completed, adjust the pH value to neutral with alkali;
[0022] The crushed and sieved pyrophyllite, quartz sand, limestone, dolomite, colemanite and boraxite are mixed with the hydrolysis solution, and the materials are uniformly dispersed in the solution under stirring conditions, and reacted at a temperature of 80-120°C for 2-4 hours to carry out copolymerization reaction, and the silanol group fully reacts with the hydroxyl group (-OH) in the raw materials to form a silicon-oxygen bond, and an appropriate amount of hydrophobic reagent is added to make the hydrophobic reagent fully react with the silanol group. After the reaction is completed, it is washed with deionized water to remove unreacted reagents and solvents, and dried in a drying oven to obtain hydrophobic glass fiber.
[0023] Compared with the prior art, the present invention has the following beneficial effects: the present invention divides the ship anti-marine biological drag-reducing paint into two components, which is convenient for operation and management, and can more effectively control the mixing and reaction process of each component; the hydrophobic glass fiber is used as the main material and is uniformly dispersed in the acrylic resin matrix through mixing; due to its ultrafine molecular structure and penetrability, the glass fiber and the resin matrix form a dense network structure, which enhances the mechanical locking; the acetone copper releases copper ions during the mixing process and forms chemical bonds with the functional groups in the resin matrix, thereby ensuring the uniform distribution and long-term effectiveness of the copper ions; the hydrophobic nano-silicon dioxide is uniformly dispersed in the polypropylene resin matrix through grinding; its ultrafine particles form a continuous nano-layer with low surface energy, which enhances the overall hydrophobic performance; and the network structure and nano-layer formed by the hydrophobic glass fiber and the hydrophobic nano-silicon dioxide are mechanically locked and chemically combined to form a multi-layered The hierarchical structure forms a gradient functional structure in the coating, which gradually enhances the hydrophobicity from the surface to the inside. The nanolayer formed by hydrophobic nano-silica provides surface hydrophobicity, and the network structure formed by hydrophobic glass fiber enhances the internal mechanical strength and durability, and enhances the hydrophobicity of the coating. It is difficult for water droplets to spread on its surface, which effectively inhibits the accumulation of dirt. Moreover, the surface energy of the coating is low, and it has strong resistance to wetting by other substances, further reducing the attachment of dirt and marine organisms. At the same time, the surface of the coating is smooth, so that the coating surface can maintain its smoothness for a long time, forming a physical barrier to prevent biological adhesion, effectively resisting electrochemical corrosion of the hull, and also reducing friction and resistance, significantly improving the drag reduction effect and anti-fouling performance of the ship in the water. In the absence of damage from external factors, it has 5 to 8 years of effective and continuous protection, improves the energy consumption indicators of the ship, and meets the "dual carbon" needs. DETAILED DESCRIPTION
[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0025] Embodiment 1:
[0026] The present embodiment provides a ship anti-marine biological drag-reducing paint, which is prepared by mixing component A and component B in a mass ratio of 1:1; wherein component A comprises material 1 and material 2 which are mixed in a mass ratio of 1:1.5, and material 1 comprises the following components by mass: 40 parts of hydrophobic glass fiber, 40 parts of xylene, and 20 parts of acetone copper; material 2 comprises the following components by mass: 50 parts of acrylic resin, 5 parts of n-butanol, and 5 parts of ethylbenzene;
[0027] Component B includes the following components by mass: 45 parts of polypropylene resin, 15 parts of filler, 25 parts of coloring pigment, 5 parts of hydrophobic nano-silicon dioxide, 10 parts of toluene, and 10 parts of additives, wherein the filler is calcium carbonate, the coloring pigment is toluene ammonia red, and the additives are antioxidants, promoters, surfactants, leveling agents, defoamers, and emulsifiers. In this embodiment, the antioxidant is 2 parts of bisphenol A antioxidant (Naugard 445), the promoter is 1 part of dimethylaniline (DMBA), the surfactant is 2 parts of dimethylsiloxane (BYK-346), the leveling agent is 1 part of acrylic leveling agent (Tego Flow300), the defoamer is 1 part of silicone defoamer (TEGO Foamex 500), and the emulsifier is 3 parts of polyoxyethylene sorbitan fatty acid ester (Tween 80).
[0028] The preparation method comprises the following steps:
[0029] S1: Prepare 40 parts of hydrophobic glass fiber, 40 parts of xylene, and 20 parts of acetone copper, dissolve the acetone copper in xylene to form a solution containing copper ions, wherein the hydrophobic glass fiber is gradually added to the mixed solution of xylene and acetone copper, and high-speed stirring or dispersion treatment is performed using a sand mill, prepare 50 parts of acrylic resin, 5 parts of n-butanol, and 5 parts of ethylbenzene, first add material 2 to the mixing equipment, and then gradually add material 1 to the melted material 2, and mix for 15 to 30 minutes. The hydrophobic glass fiber is uniformly dispersed in the acrylic resin matrix through mixing, and forms a dense network structure with the resin matrix. The acetone copper releases copper ions during the mixing process, and the copper ions react with the hydroxyl groups (-OH) of the polypropylene resin. ) undergoes a complex reaction to form a stable chemical bond, thereby enhancing the stability of acetone copper in the resin matrix, helping to prevent the premature release of copper ions and prolonging the antifouling effect; it combines with the carboxyl group (-COOH) to form a stable copper salt structure, further enhancing the stability of acetone copper in the resin matrix; this chemical bonding can prevent the migration and loss of copper ions and improve the antifouling effect; it reacts with the unsaturated double bond (C=C) to form a stable covalent bond, thereby enhancing the stability of acetone copper in the resin matrix; this covalent bonding can prevent the dissolution and release of copper ions in water; after the mixing is completed, the mixture is cooled to room temperature or an appropriate temperature, n-butanol solvent is added to dilute it, and it is filtered to obtain a paint, and the paint is dispersed by a sand mill;
[0030] S2: Prepare 45 parts of polypropylene resin, 15 parts of filler, 25 parts of coloring pigment, and 5 parts of hydrophobic nano-silicon dioxide, pre-mix the hydrophobic nano-silicon dioxide with a small amount of polypropylene resin, and then add it to the remaining polypropylene resin, filler and coloring pigment for grinding, add 10 parts of xylene and 10 parts of additives, color paint, and obtain color paste, and disperse the color paste through a sand mill. The hydrophobic nano-silicon dioxide is evenly dispersed in the polypropylene resin matrix through grinding, and its ultrafine particles form a continuous nano layer with low surface energy;
[0031] S3: input the treated color paste into the paint mixing tank, adjust it to the preset color, add the paint in step S1, and add the solvent and stir to obtain the ship anti-marine biological drag reduction paint, wherein, since the acrylic resin and the polypropylene resin are evenly mixed, the network structure and nanolayer formed by the hydrophobic glass fiber and the hydrophobic nano-silicon dioxide form a multi-level hierarchical structure through mechanical locking and chemical bonding, and a gradient functional structure is formed in the coating, so that the hydrophobic property is gradually enhanced from the surface to the inside, the nanolayer formed by the hydrophobic nano-silicon dioxide provides surface hydrophobicity, and the network structure formed by the hydrophobic glass fiber enhances the internal mechanical strength and durability, thereby enhancing the hydrophobic property of the coating.
[0032] Wherein, the preparation method of hydrophobic glass fiber comprises:
[0033] Dissolve dichlorosilane and trichlorosilane in an appropriate amount of solvent (such as ethanol, acetone, etc.), add deionized water for hydrolysis reaction, react at 40-60°C for 1-3 hours to ensure that sufficient silanol groups are generated. After the reaction is completed, adjust the pH value to neutral with a base (such as NaOH or KOH);
[0034] The crushed and sieved pyrophyllite, quartz sand, limestone, dolomite, colemanite and boraxite are mixed with the hydrolysis solution, and under stirring conditions (such as magnetic stirring or mechanical stirring), ensure that the materials are evenly dispersed in the solution, react at a temperature of 80 to 120° C. for 2 to 4 hours to carry out copolymerization reaction, ensure that the silanol group fully reacts with the hydroxyl group (-OH) in the raw materials to form a silicon-oxygen bond, add an appropriate amount of hydrophobic reagent (such as long-chain alkyl silane, fluorine-containing silane), ensure that the hydrophobic reagent fully reacts with the silanol group, and after the reaction is completed, wash with deionized water to remove unreacted reagents and solvents, and dry in a drying oven to obtain hydrophobic glass fiber.
[0035] The preparation method of hydrophobic nano-silica includes:
[0036] The base silicon dioxide is dried at a certain temperature to remove moisture, and the dried silicon dioxide particles are placed in a plasma reactor, and appropriate gas (such as hexamethyldisilazane, acrylic acid, etc.) is introduced, and the gas is excited by a high-frequency electric field to generate plasma. Under the action of the plasma, the gas molecules decompose and react with the silicon dioxide surface to introduce active groups (such as hydroxyl, carboxyl, etc.). After the reaction is completed, the silicon dioxide treated with plasma is obtained by cooling and collecting;
[0037] Dissolve an appropriate amount of hydrophobic molecules (such as octadecyltrichlorosilane, perfluorooctyltrichlorosilane, etc.) in an appropriate solvent (such as n-hexane, cyclohexane, dichloromethane, toluene, etc.) to form a solution with a concentration of 0.1 to 1% (molar percentage);
[0038] The plasma-treated silica particles are immersed in a hydrophobic molecule solution for 12 to 24 hours at room temperature or an appropriate temperature. During the immersion process, the hydrophobic molecules react with the active groups on the surface of the silica to self-assemble into a hydrophobic monolayer film.
[0039] After the reaction is completed, the silica particles are taken out from the solution and washed with a solvent (such as n-hexane) to remove the unreacted hydrophobic molecules. Then, the silica particles are dried at 60-80° C. in a vacuum or drying oven to obtain hydrophobized silica.
[0040] Embodiment 2:
[0041] The present embodiment provides a ship anti-marine biological drag-reducing paint, which is prepared by mixing component A and component B in a mass ratio of 1.2:1; wherein component A comprises material 1 and material 2 which are mixed in a mass ratio of 1:1.8, and material 1 comprises the following components by mass: 20 parts of hydrophobic glass fiber, 30 parts of xylene, and 15 parts of acetone copper; material 2 comprises the following components by mass: 40 parts of acrylic resin, 8 parts of n-butanol, and 1 part of ethylbenzene;
[0042] Component B includes the following components by mass: 30 parts of polypropylene resin, 20 parts of filler, 15 parts of coloring pigment, 2 parts of hydrophobic nano-silicon dioxide, 20 parts of xylene, and 5 parts of additives, wherein the filler is aluminum oxide, the coloring pigment is toluidine red, and the additives are antioxidants, promoters, surfactants, leveling agents, defoamers, and emulsifiers. In this embodiment, the antioxidant is 1 part of a bisphenol A antioxidant (Naugard 445), the promoter is 0.5 parts of dimethylaniline (DMBA), the surfactant is 1 part of dimethylsiloxane (BYK-346), the leveling agent is 0.5 parts of an acrylic leveling agent (Tego Flow300), the defoamer is 0.5 parts of a silicone defoamer (TEGO Foamex 500), and the emulsifier is 1.5 parts of polyoxyethylene sorbitan fatty acid ester (Tween 80).
[0043] The preparation method comprises the following steps:
[0044] S1: prepare 20 parts of hydrophobic glass fiber, 30 parts of xylene, 15 parts of acetone copper, prepare 40 parts of acrylic resin, 8 parts of n-butanol, and 1 part of ethylbenzene, first add material 2 into the mixing equipment, then gradually add material 1 into the melted material 2, and mix. After completion, cool the mixture to room temperature or a suitable temperature, add n-butanol solvent to dilute, filter, obtain paint, and disperse the paint through a sand mill;
[0045] S2: prepare 30 parts of polypropylene resin, 20 parts of filler, 15 parts of coloring pigment, and 2 parts of hydrophobic nano-silicon dioxide, pre-mix the hydrophobic nano-silicon dioxide with a small amount of polypropylene resin, and then add it to the remaining polypropylene resin, filler and coloring pigment for grinding, add 20 parts of xylene and 5 parts of additives, color paint, obtain color paste, and disperse the color paste through a sand mill;
[0046] S3: input the treated color paste into a paint mixing tank, adjust it to a preset color, add the paint in step S1, and add the solvent and stir to obtain a ship anti-marine growth drag reduction paint.
[0047] The preparation method of hydrophobic glass fiber and hydrophobic nano-silicon dioxide is the same as that in Example 1.
[0048] Example 3
[0049] The present embodiment provides a ship anti-marine biological drag-reducing paint, which is prepared by mixing component A and component B in a mass ratio of 1.5:1; component A includes material 1 and material 2 mixed in a mass ratio of 1:2, material 1 includes the following components by mass: 30 parts of hydrophobic glass fiber, 50 parts of xylene, and 10 parts of acetone copper; material 2 includes the following components by mass: 60 parts of acrylic resin, 10 parts of n-butanol, and 3 parts of ethylbenzene;
[0050] Component B includes the following components by mass: 40 parts of polypropylene resin, 25 parts of filler, 20 parts of coloring pigment, 3 parts of hydrophobic nano-silicon dioxide, 15 parts of xylene, and 15 parts of additives, wherein the filler is a mixture of toluene ammonia red and iron oxide in a molar ratio of 1:1, the coloring pigment is titanium dioxide and carbon black, and the additives are antioxidants, promoters, surfactants, leveling agents, defoamers, and emulsifiers. In this embodiment, the antioxidant is 3 parts of bisphenol A antioxidant (Naugard445), the promoter is 1.5 parts of dimethylaniline (DMBA), the surfactant is 3 parts of dimethylsiloxane (BYK-346), the leveling agent is 1 part of acrylic leveling agent (Tego Flow 300), the defoamer is 1.5 parts of silicone defoamer (TEGO Foamex 500), and the emulsifier is 5 parts of polyoxyethylene sorbitan fatty acid ester (Tween 80).
[0051] The preparation method comprises the following steps:
[0052] S1: prepare 30 parts of hydrophobic glass fiber, 50 parts of xylene, 10 parts of acetone copper, prepare 60 parts of acrylic resin, 10 parts of n-butanol, and 3 parts of ethylbenzene, first add material 2 into the mixing equipment, then gradually add material 1 into the melted material 2, and mix. After completion, cool the mixture to room temperature or a suitable temperature, add n-butanol solvent to dilute, filter, obtain paint, and disperse the paint through a sand mill;
[0053] S2: Prepare 40 parts of polypropylene resin, 25 parts of filler, 20 parts of coloring pigment, and 3 parts of hydrophobic nano-silicon dioxide, pre-mix the hydrophobic nano-silicon dioxide with a small amount of polypropylene resin, and then add it to the remaining polypropylene resin, filler and coloring pigment for grinding, add 15 parts of xylene and 15 parts of additives, color paint, obtain color paste, and disperse the color paste through a sand mill;
[0054] S3: input the treated color paste into a paint mixing tank, adjust it to a preset color, add the paint in step S1, and add the solvent and stir to obtain a ship anti-marine growth drag reduction paint.
[0055] The preparation method of hydrophobic glass fiber and hydrophobic nano-silicon dioxide is the same as that in Example 1.
[0056] Performance Testing:
[0057] The performance of the ship anti-marine biological drag reduction paints prepared in Examples 1 to 3 was tested respectively, and a coating containing copper-based chemical substances, a common Wuxi self-polishing antifouling paint and a hydrolyzed Wuxi self-polishing antifouling paint were purchased from the market as control group 1, control group 2 and control group 3. The test results are shown in Table 1 below:
[0058] Table 1
[0059]
[0060] From Table 1, the performance of the ship anti-marine biological drag-reducing paint prepared in Example 1 is better than that of Example 2 and Example 3. Two groups of control examples are set up this time. The glass fiber of Example 1 is not subjected to hydrophobic treatment as Control Example 4, and the silicon dioxide of Example 1 is not subjected to hydrophobic treatment as Control Example 5. Performance tests are carried out, and the test results are as shown in Table 2 below:
[0061] Table 2
[0062]
[0063] It can be seen from Table 2 that the performance of the ship anti-marine biofilm drag-reducing paint can be significantly improved by simultaneously treating the glass fiber and silica for hydrophobicity.
[0064] When in use, after the hull sandblasting (shot) reaches Sa2..0 or above, the surface dust is blown off and dried, and the ambient temperature (above 10°C) and humidity (less than 60) meet the construction conditions, apply according to the recommended coating thickness. After the application is completed, the coating needs to be dried for at least 24 hours to ensure that it is fully cured. During use, the coating surface should be inspected and maintained regularly. Once there are signs of attachments, consider increasing the speed for a short time or other effective methods to increase the external force so that the attachments are peeled off and prevent further growth. For organisms that have already attached, professional attachment removal tools such as soft rubber shovels, or high-pressure water guns can be used for fresh water washing to remove them.
[0065] The invention divides the ship anti-marine biological drag-reducing paint into two components, which is convenient for operation and management, and can more effectively control the mixing and reaction process of each component. The hydrophobic glass fiber is used as the main material and is uniformly dispersed in the acrylic resin matrix through mixing. Due to its ultrafine molecular structure and penetrability, the glass fiber and the resin matrix form a dense network structure, which enhances the mechanical locking. The acetone copper releases copper ions during the mixing process and forms chemical bonds with the functional groups in the resin matrix to ensure the uniform distribution and long-term effectiveness of the copper ions. The hydrophobic nano-silicon dioxide is uniformly dispersed in the polypropylene resin matrix through grinding, and its ultrafine particles form a continuous nano-layer with low surface energy, which enhances the overall hydrophobic performance. The network structure and nano-layer formed by the hydrophobic glass fiber and the hydrophobic nano-silicon dioxide form a multi-level hierarchical structure through mechanical locking and chemical bonding. A gradient functional structure is formed in the coating, so that the hydrophobic property is gradually enhanced from the surface to the inside. The nanolayer formed by hydrophobic nano-silica provides surface hydrophobicity, and the network structure formed by hydrophobic glass fiber enhances the internal mechanical strength and durability, thereby enhancing the hydrophobic property of the coating. It is difficult for water droplets to spread on its surface, which effectively inhibits the accumulation of dirt. Moreover, the surface energy of the coating is low, and it has strong resistance to wetting by other substances, further reducing the attachment of dirt and marine organisms. At the same time, the surface of the coating is smooth, so that the coating surface can maintain its finish for a long time, forming a physical barrier to prevent biological adhesion, effectively resisting electrochemical corrosion of the hull, and also reducing friction and resistance, significantly improving the drag reduction effect and anti-fouling performance of the ship in the water, and in the absence of damage from external factors, it has 5 to 8 years of effective and continuous protection, thereby increasing the service life of the ship's hull.
[0066] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A ship anti-marine organism drag-reducing paint, characterized in that: The component A and the component B are mixed in a mass ratio of 1 to 1.5:1; Wherein, component A comprises material 1 and material 2 mixed in a mass ratio of 1:1.5-2, material 1 comprises the following components by mass: 20-40 parts of hydrophobic glass fiber, 30-50 parts of xylene, and 10-20 parts of acetone copper, and material 2 comprises the following components by mass: 40-60 parts of acrylic resin, 5-10 parts of n-butanol, and 1-5 parts of ethylbenzene; Component B includes the following components by weight: 30-45 parts of polypropylene resin, 15-25 parts of filler, 15-25 parts of coloring pigment, 2-5 parts of hydrophobic nano-silicon dioxide, 10-20 parts of toluene, and 5-15 parts of additives.
2. The ship anti-marine organism drag-reducing paint according to claim 1, characterized in that: The coloring pigment includes one or more of titanium dioxide, titanium dioxide, chromium oxide, iron oxide, lemon yellow, carbon black, toluidine red, barium sulfate, and talc.
3. The ship anti-marine organism drag-reducing paint according to claim 1, characterized in that: The filler includes salts of barium, calcium, magnesium or aluminum, oxides of silicon or aluminum, or composite salts derived from salts and oxides.
4. The ship anti-marine growth drag-reducing paint according to claim 1, characterized in that: The auxiliary agent includes one or more of an antioxidant, a promoter, a surfactant, a leveling agent, a defoaming agent, and an emulsifier.
5. A method for preparing a ship anti-marine biological drag-reducing paint, characterized in that: The method comprises the following steps: S1: prepare 20-40 parts of hydrophobic glass fiber, 30-50 parts of xylene, 10-20 parts of acetone copper, prepare 40-60 parts of acrylic resin, 5-10 parts of n-butanol, and 1-5 parts of ethylbenzene, first add material 2 into a mixing device, then gradually add material 1 into the melted material 2, and mix. After completion, cool the mixture to room temperature or an appropriate temperature, add n-butanol solvent to dilute, filter, obtain a paint, and disperse the paint through a sand mill; S2: preparing 30-45 parts of polypropylene resin, 15-25 parts of filler, 15-25 parts of coloring pigment, and 2-5 parts of hydrophobic nano-silicon dioxide for grinding, adding 10-20 parts of xylene and 5-15 parts of additives, coloring paint, obtaining color paste, and dispersing the color paste through a sand mill; S3: input the treated color paste into a paint mixing tank, adjust it to a preset color, add the paint in step S1, and add a mixed solvent and stir to obtain a ship anti-marine biological drag reduction paint.
6. The method for preparing the ship anti-marine organism drag-reducing paint according to claim 1, characterized in that: In the step S2, the hydrophobic nano-silicon dioxide is pre-mixed with a small amount of polypropylene resin, and then added to the remaining polypropylene resin, filler and coloring pigment for grinding.
7. The method for preparing the ship anti-marine organism drag-reducing paint according to claim 1, characterized in that: The preparation method of the hydrophobic nano-silicon dioxide comprises: The silicon dioxide is dried at a certain temperature to remove moisture, and the dried silicon dioxide particles are placed in a plasma reactor, and a gas with active groups is introduced, and the gas is excited by a high-frequency electric field to generate plasma. Under the action of the plasma, the gas molecules are decomposed and react with the silicon dioxide surface to introduce active groups. After the reaction is completed, the silicon dioxide treated with plasma is obtained by cooling and collecting; Dissolving an appropriate amount of hydrophobic molecules in an appropriate solvent to form a solution having a molar concentration of 0.1 to 1%; The plasma-treated silica particles are immersed in a hydrophobic molecule solution for 12 to 24 hours. During the immersion process, the hydrophobic molecules react with the active groups on the surface of the silica to self-assemble into a hydrophobic monolayer film. After the reaction is completed, the silica particles are taken out from the solution, washed with a solvent to remove unreacted hydrophobic molecules, and dried in a vacuum or drying oven at 60-80° C. to obtain hydrophobized silica.
8. The method for preparing the ship anti-marine organism drag-reducing paint according to claim 1, characterized in that: The hydrophobic glass fiber is prepared by copolymerization of pyrophyllite, quartz sand, limestone, dolomite, colemanite, magnesite, dichlorosilane and trichlorosilane, and comprises the following steps: Dissolve dichlorosilane and trichlorosilane in an appropriate amount of solvent, add deionized water for hydrolysis reaction, react at 40-60°C for 1-3 hours to generate silanol groups, and after the reaction is completed, adjust the pH value to neutral with alkali; The crushed and sieved pyrophyllite, quartz sand, limestone, dolomite, colemanite and boraxite are mixed with the hydrolysis solution, and the materials are uniformly dispersed in the solution under stirring conditions. The mixture is reacted at a temperature of 80-120°C for 2-4 hours to carry out copolymerization reaction. The silanol groups react fully with the hydroxyl groups in the raw materials to form silicon-oxygen bonds. An appropriate amount of hydrophobic reagent is added to allow the hydrophobic reagent to react fully with the silanol groups. After the reaction is completed, the mixture is washed with deionized water to remove unreacted reagents and solvents, and then dried in a drying oven to obtain hydrophobic glass fibers.