An environmentally friendly marine antifouling coating suitable for long-term fresh / diluted seawater outfitting, and a preparation method and use method thereof

Abstract

The present application relates to the field of paint technology, and particularly relates to an environmentally-friendly ship antifouling paint suitable for long-term fresh water / diluted sea water outfitting, a preparation method and a use method thereof.The paint comprises the following components in parts by weight: 15-30 parts of degradable polyurethane resin, 20-25 parts of MEP resin, 10-30 parts of modified halloysite loaded with biological antifouling agent, 10-20 parts of abrasion promoter, 0-30 parts of pigment and filler, 0-10 parts of other additives, and 10-40 parts of solvent.The paint film formed by the paint has good mechanical properties and excellent antifouling performance in fresh water / diluted sea water, and the paint film after fresh water / diluted sea water outfitting can be easily removed, can play a temporary protection role on the underwater plate of the ship during long-term fresh water / diluted sea water outfitting, and does not affect the subsequent coating of the matching antifouling paint, so as to ensure that the performance of the subsequent matching antifouling paint is not affected by the long-term fresh water / diluted sea water outfitting;and the components are all biodegradable, environmentally friendly, and will not cause pollution to the environment around the shipyard.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antifouling coatings, in particular to an environmentally friendly ship antifouling coating suitable for long-term freshwater / diluted seawater outfitting, and a preparation method and use method thereof. BACKGROUND

[0002] At present, most of the commercially available marine ship antifouling coatings are designed to be applied in seawater, mainly including abrasion type antifouling coatings with rosin and its derivatives as the main binder and tin-free self-polishing antifouling coatings with side chain hydrolyzed type acrylic acid metal salt as the main binder.

[0003] However, these binders above cannot be hydrolyzed in freshwater, but will swell a lot by absorbing water. There are many ships built in freshwater in China, and long-term freshwater / diluted seawater immersion will greatly increase the risk of swelling, softening, cracking and blistering of the antifouling coating film. After the ship is in service, the antifouling period of the coating will also face great uncertainty. Moreover, the longer the freshwater / diluted seawater outfitting period, the higher the possibility of the above risks, at which time the antifouling coating has to be completely or partially removed and then recoated with antifouling coating, which not only causes economic loss, but also a large amount of coating debris containing toxic antifouling substances (such as cuprous oxide, organic antifouling agents, and non-degradable polymer resins) is removed and flows into the water, causing serious water pollution.

[0004] At present, there are few studies on antifouling coatings for long-term freshwater / diluted seawater immersion. The Chinese invention patent with application number CN201610696436.8 discloses an antifouling coating with freshwater immersion resistance, which points out that the polyvinyl ether polymer in the formula has good flexibility and is slightly soluble in water, and can be dissolved in freshwater and seawater, which to some extent alleviates the paint film defects caused by the insolubility of the paint film in freshwater. In the 6-month freshwater immersion test, the paint film is intact and has good freshwater immersion performance.

[0005] The various types of antifouling coatings for application in seawater developed for different routes and different sailing and stopping ratios are relatively mature on the market. If various types of antifouling coatings are redeveloped or the formula is optimized to meet the demand of long-term freshwater outfitting, the research and development cycle is long and the difficulty is great.

[0006] Therefore, it is of great significance to explore and develop a simple and universal solution to solve the antifouling coating defect problem caused by long-term freshwater / diluted seawater outfitting without adjusting the formula of the antifouling coating designed and developed for seawater. SUMMARY

[0007] To solve the problems of the prior art mentioned in the background art, the present application provides an environmentally friendly ship antifouling paint suitable for long-term freshwater / diluted seawater outfitting, which can temporarily protect the underwater plate of the ship during long-term freshwater / diluted seawater outfitting and does not affect the subsequent application of antifouling paint (such as the antifouling paint developed for seawater environment on the market), ensuring that the performance of the subsequent antifouling paint is not affected by long-term freshwater / diluted seawater outfitting.

[0008] The environmentally friendly ship antifouling paint suitable for long-term freshwater / diluted seawater outfitting comprises the following components by weight: 15-30 parts of degradable polyurethane resin, 20-25 parts of MEP resin, 10-30 parts of modified halloysite loaded with biological antifouling agent, 10-20 parts of abrasion promoter, 0-30 parts of pigment and filler, 0-10 parts of other additives, and 10-40 parts of solvent; wherein the preparation process of the modified halloysite loaded with biological antifouling agent is as follows: organic silane-modified halloysite is added to a biological antifouling agent ethanol solution and mixed, then the mixed system is stirred under vacuum for 20-40 minutes, then the mixed system is returned to normal pressure and stirred for 10-20 minutes, and this cycle is repeated 2-5 times, and the product is sequentially filtered, washed, freeze-dried, and ground to obtain the modified halloysite loaded with biological antifouling agent (wherein the so-called cycle refers to the cycle of the stirring treatment step composed of the two processes of stirring treatment under vacuum and stirring treatment under normal pressure for 2-5 times).

[0009] In some embodiments, the preparation process of the modified halloysite loaded with biological antifouling agent is as follows:

[0010] The halloysite is soaked in an acid solution, shaken every (6-12) hours, repeated 2-20 times, sequentially filtered, washed with an ethanol solution, and vacuum dried to obtain acid-activated halloysite;

[0011] A certain amount of acid-activated halloysite is dispersed in anhydrous toluene, a silane coupling agent is added and stirred uniformly, and stirred under heating at 110-130℃ for 6-24 hours of reflux. After the reaction is completed and the temperature is lowered to room temperature, the product is washed with toluene multiple times, and then the product is sequentially vacuum dried at 80-100℃ for 6-24 hours, crushed, and sieved to obtain organic silane-modified halloysite;

[0012] A certain amount of organic silane-modified halloysite is added to a biological antifouling agent ethanol solution and mixed uniformly, the mixed system is stirred under vacuum for 20-40 minutes, then the mixed system is returned to normal pressure and stirred for 10-20 minutes, and this cycle is repeated 2-5 times, and the product is sequentially filtered, washed, freeze-dried, and ground to obtain the modified halloysite loaded with biological antifouling agent.

[0013] In some embodiments, the ratio of the acidified halloysite to the silane coupling agent is 1 g : (0.01-0.05) mol; the ratio of the silane coupling agent to the anhydrous toluene is (0.1-1) mol: 1 L; the ratio of the organosilane-modified halloysite to the bioantifouling agent is 1 : (1-5); and the mass concentration of the bioantifouling agent in the ethanol solution of the bioantifouling agent is (10-30) %.

[0014] In some embodiments, the acid solution is one of a hydrochloric acid solution, a sulfuric acid solution, and an acetic acid solution; the concentration of the hydrochloric acid solution is 0.1-10 mol / L, the concentration of the sulfuric acid solution is 0.1-10 mol / L, and the concentration of the acetic acid solution is 0.1-10 mol / L; and the silane coupling agent is one or a combination of 3-(2,3-epoxypropoxy)propyl trimethoxysilane, 3-(2,3-epoxypropoxy)propyl triethoxysilane, 3-(methacryloyl)propyl trimethoxysilane, 3-(methacryloyl)propyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, (3-mercaptopropyl)trimethoxysilane, and (3-mercaptopropyl)triethoxysilane.

[0015] In some embodiments, the molecular structure of the bioantifouling agent is:

[0016]

[0017] The molecular structure of the bioantifouling agent consists of a benzene ring, a phenolic hydroxyl group, a methoxy group, a propionyl group, an amine group, and R1, wherein R1 is a linear or branched alkyl chain of C1-C 10 ; and some groups in the molecular structure are derived from the natural active ingredient paeonol, which is extracted from the root bark or whole grass of Paeonia suffruticosa, Paeonia lactiflora, and Xu Changqing plants, and additionally contains a Mannich base structure and an alkyl amine structure.

[0018] In some embodiments, the degradable polyurethane resin is a polyurethane containing a degradable polyester segment, wherein the mass content of the degradable polyester segment is 10-90 %, and the degradable polyester segment is one or a combination of poly(caprolactone), poly(lactide), poly(ethylene glycol adipate), poly(diethylene glycol adipate), poly(caprolactone-lactide), poly(caprolactone-ethylene glycol), and poly(lactide-ethylene glycol); and the MEP resin is prepared by aldol condensation of acrolein and vinyl ethyl ether.

[0019] In some embodiments, the abrasion promoter is anhydrous calcium sulfate; the color filler is one or a combination of black iron oxide, carbon black, red iron oxide, toluidine red, yellow iron oxide, phthalocyanine blue, phthalocyanine green, titanium dioxide, dolomite powder, talc powder, and mica powder, and the particle size of the color filler is ≤50 μm.

[0020] In some embodiments, the other auxiliary agent is one or more of a combination of polyamide wax, organic bentonite, fumed silica, hydrogenated castor oil; and the solvent is one or more of a combination of xylene, propylene glycol methyl ether acetate, methyl isobutyl ketone, butanone, butyl acetate, n-butanol, ethyl acetate.

[0021] The application also provides a preparation method of the environmentally-friendly ship antifouling paint suitable for long-term freshwater / brackish water outfitting, which comprises the following steps:

[0022] The modified halloysite loaded with the biological antifouling agent and the first part of the solvent are mixed and uniformly dispersed to obtain a modified halloysite dispersion liquid loaded with the biological antifouling agent;

[0023] The degradable polyurethane resin, the MEP resin, the abrasion promoter, the other auxiliary agent and the second part of the solvent are mixed and uniformly dispersed, and then the pigments and fillers are dispersed or ground at a high speed to a fineness of less than 80 microns, and filtered to obtain a resin powder dispersion liquid; wherein the sum of the amounts of the first part of the solvent and the second part of the solvent is equal to the total amount of the solvent;

[0024] The modified halloysite dispersion liquid loaded with the biological antifouling agent and the resin powder dispersion liquid are mixed, and then uniformly dispersed and filtered to obtain the environmentally-friendly ship antifouling paint.

[0025] The application also provides a use method of the environmentally-friendly ship antifouling paint suitable for long-term freshwater / brackish water outfitting, which comprises the following steps:

[0026] The environmentally-friendly ship antifouling paint is coated:

[0027] Firstly, the matched coating is coated according to the coating process requirements before the freshwater outfitting; the matched coating is coated by using any one of two coating modes, wherein the first coating mode is to complete 1-3 coats of epoxy primer, and the second coating mode is to complete 1-3 coats of epoxy primer and then coat 1 coat of connecting paint; then, according to the freshwater outfitting period, the environmentally-friendly ship antifouling paint is coated for 1-2 coats, and the coating thickness is 50-120 microns;

[0028] The environmentally-friendly ship antifouling paint is removed

[0029] The coating can be easily washed and removed by using a high-pressure water gun, and the bottom complete coating is exposed; then, the subsequent matched antifouling paint (the antifouling paint developed for seawater environment on the market) is coated according to the coating process requirements.

[0030] Compared with the prior art, the environmentally-friendly ship antifouling paint suitable for long-term freshwater / brackish water outfitting has the following beneficial effects:

[0031] The paint film formed by the coating has good mechanical properties, excellent antifouling performance in fresh water / brackish water, and can be easily removed after fresh water / brackish water outfitting, can play a temporary protection role on the underwater plate of the ship during long-term fresh water / brackish water outfitting, and does not affect the subsequent coating of the matching antifouling coating (for example, the antifouling coating developed for seawater environment on the market), ensuring that the performance of the subsequent matching antifouling coating is not affected by long-term fresh water / brackish water outfitting; the components of the antifouling coating are biodegradable and environmentally friendly, and do not pollute the environment around the shipyard. DETAILED DESCRIPTION

[0032] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0033] The present application provides an operation example of a preparation method of an environmentally friendly ship antifouling coating suitable for long-term fresh water / brackish water outfitting, comprising the following steps:

[0034] Step 1

[0035] Mix and uniformly disperse the modified halloysite loaded with a biological antifouling agent and a first part of solvent to obtain a modified halloysite dispersion liquid loaded with a biological antifouling agent.

[0036] Step 2

[0037] Mix and uniformly disperse the degradable polyurethane resin, the MEP resin, the abrasion promoter, other additives, and a second part of solvent, then add the pigments and fillers and disperse or grind at high speed to a fineness of 80 μm or less, and filter to obtain a resin powder dispersion liquid; wherein the sum of the amounts of the first part of solvent and the second part of solvent is equal to the total amount of solvent.

[0038] Step 3

[0039] Mix the modified halloysite dispersion liquid loaded with a biological antifouling agent and the resin powder dispersion liquid, and then uniformly disperse and stir, and filter to obtain an environmentally friendly ship antifouling coating.

[0040] The formula of the coating is:

[0041] The coating comprises the following components by weight: degradable polyurethane resin 15-30 parts, MEP resin 20-25 parts, modified halloysite loaded with a biological antifouling agent 10-30 parts, abrasion promoter 10-20 parts, pigments and fillers 0-30 parts, other additives 0-10 parts, and solvent 10-40 parts.

[0042] Wherein, for each raw material component:

[0043] The degradable polyurethane resin is a polyurethane containing degradable polyester segments, wherein the mass content of the degradable polyester segments is 10% to 90%, preferably 70% to 80%, and the degradable polyester segments are one or more of poly(caprolactone), poly(lactide), poly(ethylene adipate), poly(diethylene adipate), poly(caprolactone-lactide), poly(caprolactone-ethylene glycol), and poly(lactide-ethylene glycol).

[0044] The MEP resin is prepared by aldol condensation reaction of propylene aldehyde and vinyl ether, and specifically refers to the new resin described in the Chinese patent application No. CN200710026054.5, entitled "Production process of a new resin". The production steps of the condensation reaction of the new resin are as follows:

[0045] (1) The vinyl ether is added into a condensation kettle, then the catalyst zinc salt or aluminum salt is put into the kettle, the stirring is started, then the propylene aldehyde is put into the condensation kettle, the valve is closed after the feeding, at the same time, the jacket of the condensation kettle is heated with hot water, the temperature is slowly increased, and the condenser above the condensation kettle is cooled to make the solution reflux, when the temperature in the condensation kettle is increased to 60-65℃, the heating is stopped, the temperature is cooled to below 30℃, then the material is pumped into a distillation kettle;

[0046] (2) The obtained material is subjected to normal pressure distillation to 230-240℃, the valve of the storage tank above the distillation kettle is opened, the blocking resin is put into the distillation kettle, after the co-melting, all the fractions below 240℃ are collected, the by-product 2-ethoxy-3,4-dihydropyran is obtained and put into the storage tank; the high polymer remaining in the distillation kettle is naturally cooled to 200℃, then the material is discharged, and the MEP resin is obtained;

[0047] Wherein, the gram-mole ratio of the raw materials propylene aldehyde, vinyl ether and catalyst is 1:1.05-1.15:0.010-0.020.

[0048] Wherein, the operation example of the preparation method of the modified halloysite loaded with the biological antifouling agent is as follows, the modified halloysite loaded with the biological antifouling agent is prepared by vacuum adsorption method:

[0049] Step (1)

[0050] The halloysite is soaked in an acid solution, shaken every (6-12) hours, repeated for 2-20 times, and sequentially filtered, washed with ethanol solution, and vacuum dried to obtain the acid-activated halloysite.

[0051] Step (2)

[0052] A certain amount of acid-activated halloysite is dispersed in anhydrous toluene, a silane coupling agent is added and stirred uniformly, and the mixture is stirred under heating at 110-130℃ for 6-24 hours. After the reaction is completed and the temperature is lowered to room temperature, the product is washed with toluene for several times, and then the product is vacuum-dried at 80-100℃ for 6-24 hours, crushed, and sieved to obtain organosilane-modified halloysite. The ratio of the acid-activated halloysite to the silane coupling agent is 1g:(0.01-0.05)mol, and the ratio of the silane coupling agent to the anhydrous toluene is (0.1-1)mol:1L.

[0053] Step (3)

[0054] A certain amount of organosilane-modified halloysite is added to an ethanol solution of a biological antifouling agent and mixed uniformly. The mixture is stirred under vacuum for 20-40 minutes, and then the normal pressure is restored and the mixture is stirred for 10-20 minutes. The cycle is repeated for 2-5 times. The product is filtered, washed, freeze-dried, and ground to obtain modified halloysite loaded with a biological antifouling agent.

[0055] The mass ratio of the organosilane-modified halloysite to the biological antifouling agent is 1:(1-5), and the mass concentration of the biological antifouling agent in the ethanol solution is (10-30)%. The acid solution is one of a hydrochloric acid solution, a sulfuric acid solution, and an acetic acid solution. The concentration of the hydrochloric acid solution is 0.1-10mol / L, the concentration of the sulfuric acid solution is 0.1-10mol / L, and the concentration of the acetic acid solution is 0.1-10mol / L. The silane coupling agent is one or a combination of multiple of 3-(2,3-epoxypropoxy)propyl trimethoxysilane, 3-(2,3-epoxypropoxy)propyl triethoxysilane, 3-(methacryloyl)propyl trimethoxysilane, 3-(methacryloyl)propyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, (3-mercaptopropyl)trimethoxysilane, and (3-mercaptopropyl)triethoxysilane.

[0056] The biological antifouling agent is the biological antifouling agent described in the Chinese invention patent with the application number CN201410836582.7 and the title "Antifouling Coating Containing Biological Antifouling Agent and Preparation Method Thereof". The biological antifouling agent can be quickly degraded in a natural seawater environment, and the half-life is less than 72 hours. The biological antifouling agent can be digested and absorbed by microorganisms as a carbon source and a nitrogen source. The molecular structure of the biological antifouling agent is:

[0057]

[0058] The molecular structure of the biological antifouling agent is composed of a benzene ring, a phenolic hydroxyl group, a methoxy group, a propionyl group, an amine group, and R1, wherein R1 is C1-C 10linear or branched alkyl chain; part of the groups in the molecular structure is derived from natural active ingredient paeonol, which is extracted from the root bark or whole grass of Paeonia suffruticosa, Paeonia lactiflora and Radix Kuangqianqin plants, and additionally contains a Mannich base structure and an alkylamine structure.

[0059] The preparation process of the bio-antifouling agent is as follows: the extracted natural molecule paeonol is mixed with trioxane and alkylamine in anhydrous ethanol, and a Mannich reaction is carried out under the catalysis of concentrated hydrochloric acid, the weight ratio of the components is paeonol: trioxane: alkylamine: anhydrous ethanol: concentrated hydrochloric acid = 1: (1-4): (1-2): 30: (0.1-1), the reaction temperature is 25-140 DEG C, the reaction time is 1-48 hours, after the reaction is completed, the obtained product is neutralized to pH = 7 with a 10% NaHCO3 aqueous solution, and then the bio-antifouling agent is prepared by recrystallizing and purifying the separated product with anhydrous ethanol. The weight percentage concentration of the concentrated hydrochloric acid is 37%.

[0060] The application also provides a use method of the environmentally-friendly ship antifouling paint suitable for long-term fresh water / diluted sea water outfitting.

[0061] 1) Coating of the environmentally-friendly ship antifouling paint

[0062] Firstly, the matching coating is coated according to the coating process requirements of the shipyard before fresh water outfitting. Generally, two coating methods can be selected before fresh water outfitting: 1) coating of 1-3 coats of epoxy primer, 2) coating of 1-3 coats of epoxy primer and 1 coat of connecting paint, and one of the coating methods is selected according to actual needs. Then, 1-2 coats of the environmentally-friendly antifouling paint of the application are coated according to the fresh water outfitting period, and the coating thickness is 50-120 mu m.

[0063] 2) Removal of the environmentally-friendly ship antifouling paint

[0064] After the fresh water outfitting, the ship is docked again, the film thickness of the antifouling coating is continuously consumed due to self-hydrolysis / degradation, the film thickness is completely consumed or consumed to a thin layer when the ship is docked again, the coating can be easily washed and removed by using a high-pressure water gun, and the bottom complete coating is exposed. Subsequently, the subsequent matching antifouling paint (the antifouling paint developed for sea water environment on the market) is coated according to the coating process requirements of the shipyard.

[0065] The application also provides the following examples and comparative examples:

[0066] 1. The application provides the following preparation examples and comparative examples of the modified halloysite loaded with the bio-antifouling agent, and the preparation parameters and product loading rate data are as follows, as shown in Table 1:

[0067] Table 1

[0068]

[0069] In Table 1, the antifouling agent loading rate refers to the mass ratio of the antifouling agent to the modified halloysite loaded with the biological antifouling agent.

[0070] (1) The modified halloysite loaded with the biological antifouling agent was prepared according to the parameters in Table 1, and the preparation steps were as follows:

[0071] 1) 12 g of halloysite was soaked in 200 ml of an acid solution, and was shaken every 12 hours. After repeated soaking, the halloysite was filtered, washed with an ethanol solution (50% by volume) for 5 times, vacuum dried at 90°C for 12 hours, crushed, and sieved to obtain acid-activated halloysite;

[0072] 2) 11 g of the acid-activated halloysite was added to 300 mL of a 0.4 mol / L 3-(2,3-epoxypropoxy) propyl trimethoxysilane anhydrous toluene solution, and was stirred uniformly. Then, the temperature was increased to 130°C, and the mixture was stirred and condensed under reflux for 12 hours in an anhydrous environment. Then, the temperature was decreased to room temperature, the mixture was washed with toluene for 3 times, vacuum dried at 90°C for 12 hours, crushed, and sieved to obtain organosilane-modified halloysite;

[0073] 3) 10 g of the organosilane-modified halloysite was added to 100 g of an ethanol solution (20% by mass) of the biological antifouling agent, and was mixed uniformly. The mixture was stirred under vacuum for 40 minutes, and then the pressure was restored to normal pressure and the mixture was stirred for 20 minutes. The cycle was repeated for 3 times. After filtration, washing, freeze-drying, and grinding, the modified halloysite loaded with the biological antifouling agent was obtained.

[0074] In addition, the modified halloysite of Comparative Example a1 was not loaded with the biological antifouling agent, that is, in the preparation process, the organosilane-modified halloysite was added to 100 g of ethanol for mixing, and no biological antifouling agent was added.

[0075] (2) As can be seen from the data in Table 1:

[0076] The modified halloysite loaded with the biological antifouling agent prepared in Example A4 has a high antifouling agent loading rate. In the product prepared in Comparative Example a1, the loading rate of the biological antifouling agent is 0.

[0077] 2. The present application provides an example of an environmentally friendly ship antifouling coating prepared from the modified halloysite loaded with the biological antifouling agent in Example A4 and its comparative example, as shown in Table 2:

[0078] Table 2

[0079]

[0080]

[0081] (1) The raw materials used in the above examples and comparative examples are selected as follows (the components in each example and comparative example are provided by the same company and the same series of products):

[0082] The selected biological antifouling agent is prepared according to Example 1 of Chinese Invention Patent No. CN201410836582.7;

[0083] The selected MEP resin is prepared by aldol condensation reaction of propylene aldehyde and vinyl ether, and is prepared according to Example 1 of Chinese Invention Patent No. CN200710026054.5;

[0084] The selected degradable polyurethane resin is a polyurethane containing a degradable polyester segment, wherein the content of the degradable polyester segment is 80%, and the degradable polyester segment is polycaprolactone.

[0085] The selected abrasion promoter is anhydrous calcium sulfate.

[0086] The selected pigment and filler is iron oxide red and talc powder, and the mass ratio is 1:1, and the particle size is ≤50 μm.

[0087] The selected other auxiliary agent is hydrogenated castor oil.

[0088] The selected solvent is a combination of dimethylbenzene and n-butanol, and the mass ratio is 2:1.

[0089] (2) The preparation method of the coating in Table 2 is as follows:

[0090] Step 1

[0091] The modified halloysite loaded with the biological antifouling agent and the first part of the solvent are mixed and uniformly dispersed to obtain a modified halloysite dispersion liquid loaded with the biological antifouling agent.

[0092] Step 2

[0093] The degradable polyurethane resin, the MEP resin, the abrasion promoter, the other auxiliary agent, and the second part of the solvent are mixed and uniformly dispersed, and then the pigment and filler are dispersed or ground at high speed to a fineness of 80 μm or less, and filtered to obtain a resin powder dispersion liquid; wherein the total amount of the first part of the solvent and the second part of the solvent is equal to the total amount of the solvent.

[0094] Step 3

[0095] After the modified halloysite dispersion liquid loaded with the biological antifouling agent and the resin powder dispersion liquid are mixed, they are uniformly dispersed by stirring and filtering to obtain an environmentally friendly ship antifouling coating.

[0096] 3. The test results of the properties of Examples B1-B3 and Comparative Examples b1-b11 are shown in Table 3:

[0097] Table 3

[0098]

[0099]

[0100] In Table 3, the coating of the examples and the comparative examples is as follows: epoxy primer 2 coats + connecting paint 1 coat + antifouling coating prepared by the examples and the comparative examples, thickness 90-100 μm; wherein, the comparative example b11 uses commercially available traditional zinc acrylate self-polishing antifouling coating containing cuprous oxide.

[0101] (1) The specific test method is as follows:

[0102] 1) Initial adhesion: refer to ASTM D4541-09;

[0103] 2) Fouling coverage area after fresh water immersion: the immersion test method refers to GB / T 5370, the immersion site is a fresh water area near a shipyard at the estuary of the Yangtze River, the immersion time is 18 months, and the evaluation method is to take out the sample plate, estimate the fouling area on the surface of the sample plate, and obtain the "fouling coverage area after 18 months of fresh water immersion" data;

[0104] 3) Coverage area: after 18 months of fresh water immersion, the sample plate is taken out, the area of the antifouling coating remaining on the surface of the sample plate is estimated, and the "antifouling coating coverage area after 18 months of fresh water immersion" data is obtained. The surface is washed with a high-pressure water gun, and after washing, the area of the antifouling coating remaining on the surface of the sample plate is estimated, and the "antifouling coating coverage area after surface washing" data is obtained. The area of the fouling remaining on the surface of the sample plate is estimated, and the "fouling coverage area after surface washing" data is obtained.

[0105] (2) Analysis of the above data shows that:

[0106] The antifouling coating coverage area of the examples B1-B3 after 18 months of fresh water immersion is high, 97%-100%, and the fouling coverage area is zero, and the antifouling performance under long-term fresh water immersion treatment is good; and the coating can be completely removed clean under high-pressure water gun washing.

[0107] Compared with the examples, the antifouling coating of the comparative examples b1-b2 is seriously powdered after 30 days of fresh water immersion, and the fouling coverage area increases after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor, the antifouling coating coverage area decreases, which is caused by poor coating mechanics and serious abrasion; after surface washing, the fouling is still covered, so the high-pressure water gun washing cannot remove the fouling.

[0108] Compared with the example, the biodegradable polyurethane resin of the comparative example b3 replaces the MEP resin in the example B1, and the fouling coverage area becomes larger after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor; and after surface flushing, the antifouling coating and the fouling are still covered, so the high-pressure water gun flushing cannot completely remove the coating and the fouling.

[0109] Compared with the example, the biodegradable polyurethane resin and the MEP resin of the comparative example b4 are added in a proportion outside the range defined in the application, and the antifouling coating appears powdering phenomenon after 30 days of fresh water immersion, and the fouling coverage area increases and the antifouling coating coverage area decreases after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor; and after surface flushing, the fouling is still covered, so the high-pressure water gun flushing cannot completely remove the fouling.

[0110] Compared with the example, the biodegradable polyurethane resin and the MEP resin of the comparative example b5 are added in a proportion outside the range defined in the application, and the fouling coverage area increases after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor; and after surface flushing, the fouling and the coating are still covered, so the high-pressure water gun flushing cannot completely remove the fouling and the coating.

[0111] Compared with the example, the modified halloysite of the comparative example b6 does not load the biological antifouling agent, the comparative example b7 directly adds the biological antifouling agent, and the addition amount of the modified halloysite loaded with the biological antifouling agent of the comparative example b8 is lower than the range defined in the application, and the fouling coverage area increases after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor; and after surface flushing, the fouling is still covered, so the high-pressure water gun flushing cannot completely remove the fouling.

[0112] In addition, the addition amount of the modified halloysite loaded with the biological antifouling agent opposite to the comparative example b8 is higher than the range defined in the application, which not only causes waste of the antifouling agent, but also makes the pigment and filler volume concentration (PVC) too high, resulting in poor film forming property of the coating and poor mechanical property.

[0113] Among them, due to the poor antifouling performance of the comparative examples b1-b8 under long-term fresh water immersion treatment, part of the fouling adheres to and penetrates into the coating under the antifouling coating, so the high-pressure water gun flushing cannot completely remove the fouling.

[0114] Compared with the example, the comparative example b9 does not add the abrasion promoter, and the fouling coverage area slightly increases after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor; and after surface flushing, the coating is still covered, so the high-pressure water gun flushing cannot completely remove the coating.

[0115] Compared with the example, the abrasion promoter added in the comparative example B10 is less than the limited range, and after surface flushing, the coating is still covered, so the high-pressure water gun flushing cannot completely remove the coating; the abrasion promoter added in the comparative example B10 is higher than the limited range of the application, on the one hand, the coating is abraded too fast, and on the other hand, the PVC content is higher, and the mechanical properties of the coating are poor.

[0116] Compared with the example, the abrasion promoter added in the comparative example B10 is less than the limited range, and after surface flushing, the coating is still covered, so the high-pressure water gun flushing cannot completely remove the coating; the abrasion promoter added in the comparative example B10 is higher than the limited range of the application, on the one hand, the coating is abraded too fast, and on the other hand, the PVC content is higher, and the mechanical properties of the coating are poor.

[0117] 4. The test results of the environmentally friendly ship antifouling coating of the example B1, the comparative example B1 and the comparative example B11 on different substrates are shown in Table 4:

[0118] Table 4

[0119]

[0120] The primer is specifically a general epoxy primer, and the connecting paint is a general epoxy connecting paint.

[0121] From the above data, it can be seen that:

[0122] The antifouling coating of the primer 2 coats + the example B1 has a 100% coverage area of the antifouling coating after 18 months of fresh water immersion, and the fouling coverage area is zero, and the antifouling performance under long-term fresh water immersion treatment is good; and the coating can be completely removed clean under high-pressure water gun flushing.

[0123] The antifouling coating of the primer 2 coats + the comparative example B1 has a low adhesion value at the initial adhesion test, and after 30 days of fresh water immersion, the coating appears serious powdering, and the fouling coverage area increases after 18 months of fresh water immersion, indicating that the antifouling performance under long-term fresh water immersion treatment is poor; and after surface flushing, the fouling is difficult to clean.

[0124] The antifouling coating of the primer 2 coats + the comparative example B11 has a low adhesion value at the initial adhesion test, and after 30 days of fresh water immersion, the primer and the antifouling coating are separated, and no adhesion test data can be obtained; after 18 months of fresh water immersion, the antifouling coating appears blistering and cracking, and after surface flushing, part of the coating at the blistering and cracking position can be flushed down, but most of the coating is difficult to clean.

[0125] In summary, the paint film formed by the paint has good mechanical properties, excellent antifouling performance in fresh water / diluted seawater, and can be easily removed after fresh water / diluted seawater outfitting, can play a temporary protection role on the underwater plate of the ship during long-term fresh water / diluted seawater outfitting, and does not affect the subsequent matching antifouling paint coating, ensures that the performance of the subsequent matching antifouling paint is not affected by long-term fresh water / diluted seawater outfitting; the components of the antifouling paint are biodegradable, environmentally friendly, and will not pollute the environment around the shipyard.

[0126] In summary, the environmentally friendly ship antifouling paint suitable for long-term fresh water / diluted seawater outfitting has at least the following design concepts and beneficial effects:

[0127] (1) The degradable polyurethane resin and MEP resin are used as the coating base composite resin, the existence of amino ester bond in the structure of the degradable polyurethane resin makes it have good adhesion effect with the epoxy primer and the connecting paint; the MEP resin is a new type of resin with antibacterial effect, and its antialgal and antibacterial effect in fresh water is particularly outstanding, the combination of the two resins makes the film forming property of the coating good and the mechanical property excellent, after soaking in fresh water, both resins can be hydrolyzed / degraded, and by adjusting the blending ratio of the two, a suitable coating abrasion rate can be obtained. In addition, the anhydrous calcium sulfate, which is a kind of abrasion promoter, has the characteristics of small density and slightly soluble in water, and plays a role in promoting abrasion in the coating.

[0128] (2) The biological antifouling agent is a new type of non-toxic antifouling compound, and the pure biological antifouling agent is easy to crystallize and precipitate directly added into the coating, and is loaded on the modified halloysite, which solves the problem of excessive fineness of the coating caused by the crystallization and precipitation of the antifouling agent, and the problem of "burst release" of the antifouling agent; in addition, the antifouling agent needs to undergo "pipe wall desorption-pipe cavity migration-molecular chain migration" before being released, which plays a role in controlling the release of the antifouling agent. There are fewer kinds of fouling organisms in fresh water / diluted seawater, but there are also many algae, shellfish (clams) and other fouling organisms that are difficult to remove after attachment, and a single MEP resin cannot meet the antifouling requirements, the combination of the biological antifouling agent and the MEP resin can improve the antifouling performance of the coating in fresh water / diluted seawater.

[0129] (3) The antifouling coating continuously wears the film thickness by itself, and the film thickness will be completely consumed or consumed to a thin layer when re-docking, and the coating can be easily washed away by using a high-pressure water gun, and the bottom complete coating is exposed. Since the components of the coating are all environmentally friendly materials and can be biodegraded, the substances worn off or washed off are non-toxic and harmless, and will not pollute the nearby water.

[0130] In summary, the paint film formed by the antifouling paint has good mechanical properties, excellent antifouling performance in fresh water / diluted seawater, and can be easily removed after fresh water / diluted seawater installation, can temporarily protect the underwater plate of the ship during long-term fresh water / diluted seawater installation, and does not affect the subsequent matching antifouling paint coating, ensures that the performance of the subsequent matching antifouling paint is not affected by long-term fresh water / diluted seawater installation; the components of the antifouling paint are biodegradable, environmentally friendly, and will not pollute the environment around the shipyard.

[0131] It should be noted that:

[0132] In this paper, "~" is used to represent a numerical range, and the range represented by this expression includes both end point values.

[0133] In addition to the actual choices embodied in the above specific embodiments, the formula of the paint includes the following components by weight fraction: 15-30 parts of degradable polyurethane resin, 20-25 parts of MEP resin, 10-30 parts of modified halloysite loaded with biological antifouling agent, 10-20 parts of abrasion promoter, 0-30 parts of pigment and filler, 0-10 parts of other additives, and 10-40 parts of solvent. The above formula range can be used in the specific implementation of the present application, including but not limited to the above embodiment schemes.

[0134] The specific parameters or some commonly used reagents in the above examples are specific embodiments or preferred embodiments under the concept of the present application, but not limited thereto; those skilled in the art can make adaptive adjustments within the concept and protection scope of the present application. In addition, if not specially stated, the raw materials used can be conventional commercially available products in the art, or prepared by conventional methods in the art.

[0135] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, but not limited thereto; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solution deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting, characterized in that, By weight, it includes the following components: 15-30 parts of biodegradable polyurethane resin, 20-25 parts of MEP resin, 10-30 parts of modified halloysite loaded with biofouling agent, 10-20 parts of abrasion accelerator, 0-30 parts of pigments and fillers, 0-10 parts of other additives, and 10-40 parts of solvent. The MEP resin is prepared by the condensation reaction of acrolein and vinyl ether aldehyde; The preparation process of the modified halloysite loaded with biofouling agent is as follows: Organosilylated halloysite was added to an ethanol solution of a biofouling agent and mixed. The mixture was then stirred under vacuum for 20–40 minutes. The mixture was then restored to normal pressure and stirred for 10–20 minutes. This cycle was repeated 2–5 times. The product was then filtered, washed, and freeze-dried to obtain modified halloysite loaded with the biofouling agent.

2. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in claim 1, characterized in that: The preparation process of the modified halloysite loaded with biofouling agent is as follows: Halloysite was soaked in an acid solution and shaken every 6 to 12 hours, repeated 2 to 20 times. It was then filtered, washed with ethanol solution, and dried under vacuum to obtain acid-activated halloysite. A certain amount of acid-activated halloysite was dispersed in anhydrous toluene, and a silane coupling agent was added and stirred evenly. The mixture was stirred and refluxed at 110–130°C for 6–24 hours. After the reaction was completed and cooled to room temperature, the product was washed with toluene several times. Then, the product was vacuum dried at 80–100°C for 6–24 hours, pulverized, and sieved to obtain organosilylated modified halloysite. A certain amount of organosilylated halloysite was added to an ethanol solution of a biofouling agent and mixed evenly. The mixture was then stirred under vacuum for 20–40 minutes. The mixture was then restored to normal pressure and stirred for 10–20 minutes. This cycle was repeated 2–5 times. The product was then filtered, washed, freeze-dried, and ground to obtain modified halloysite loaded with the biofouling agent.

3. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in claim 2, characterized in that: The ratio of the acidified halloysite to the silane coupling agent is 1 g: (0.01–0.05) mol; The ratio of the silane coupling agent to the anhydrous toluene is (0.1–1) mol: 1 L; The mass ratio of the organosilicon-modified halloysite to the biofouling agent is 1:(1-5); In the ethanol solution of the biofouling agent, the mass concentration of the biofouling agent is (10-30)%.

4. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in any one of claims 1-3, characterized in that: The acid solution is one of hydrochloric acid solution, sulfuric acid solution, and acetic acid solution; wherein the concentration of the hydrochloric acid solution is 0.1-10 mol / L, the concentration of the sulfuric acid solution is 0.1-10 mol / L, and the concentration of the acetic acid solution is 0.1-10 mol / L. The silane coupling agent is one or more combinations of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, 3-(methacryloyl)propyltrimethoxysilane, 3-(methacryloyl)propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, and (3-mercaptopropyl)triethoxysilane.

5. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in claim 2, characterized in that: The molecular structure of the biofouling agent is as follows: ； The biofouling agent has a molecular structure consisting of a benzene ring, a phenolic hydroxyl group, a methoxy group, a propionyl group, an amino group, and R1, wherein R1 is C1-C. 10 It contains linear or branched alkyl chains; some groups in the molecular structure are derived from the natural active ingredient paeonol, which is extracted from the root bark or whole herb of peony, herbaceous peony and cynanchum paniculatum. It also contains Mannich base structure and alkylamine structure.

6. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in claim 1, characterized in that: The biodegradable polyurethane resin is a polyurethane containing biodegradable polyester segments, wherein the mass content of biodegradable polyester segments is 10% to 90%, and the biodegradable polyester segments are polymerized from one or more of polycaprolactone, polylactide, polyethylene adipate, diethylene adipate, poly(caprolactone-lactide), poly(caprolactone-ethylene glycol), and poly(lactide-ethylene glycol).

7. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in claim 1, characterized in that: The abrasion accelerator is anhydrous calcium sulfate; The pigments and fillers are one or more combinations of iron oxide black, carbon black, iron oxide red, toluidine red, iron oxide yellow, phthalocyanine blue, phthalocyanine green, titanium dioxide, dolomite powder, talc powder, and mica powder, and the particle size of the pigments and fillers is ≤50μm.

8. The environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in claim 1, characterized in that: The other additives are one or more combinations of polyamide wax, organobentonite, fumed silica, and hydrogenated castor oil. The solvent is one or a combination of xylene, propylene glycol methyl ether acetate, methyl isobutyl ketone, butanone, butyl acetate, n-butanol, and ethyl acetate.

9. A method for preparing an environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in any one of claims 1-8, characterized in that, Includes the following steps: The modified halloysite loaded with the biofouling agent was mixed and dispersed evenly with the first portion of the solvent to obtain a modified halloysite dispersion loaded with the biofouling agent; The biodegradable polyurethane resin, MEP resin, abrasion accelerator, other additives, and the second solvent are mixed and dispersed evenly. Then, pigments and fillers are added and dispersed at high speed or ground to a fineness of less than 80 μm. After filtration, a resin powder dispersion is obtained. The sum of the amounts of the first solvent and the second solvent is equal to the total amount of solvent. After mixing the modified halloysite dispersion loaded with the biofouling agent and the resin powder dispersion, the mixture is stirred and dispersed evenly, and then filtered to obtain an environmentally friendly marine antifouling coating.

10. A method for using an environmentally friendly antifouling coating for long-term freshwater / freshwater outfitting as described in any one of claims 1-8, characterized in that, Includes the following steps: Application of the aforementioned environmentally friendly antifouling coating for ships: First, apply the matching coating according to the painting process requirements before freshwater outfitting; The coating method can be any one of two coating methods. The first coating method is to complete 1 to 3 coats of epoxy primer. The second coating method is to complete 1 to 3 coats of epoxy primer and then apply 1 coat of bonding paint. Then, according to the freshwater outfitting cycle, apply 1 to 2 coats of the environmentally friendly marine antifouling coating with a coating thickness of 50 to 120 μm. Removal of the aforementioned environmentally friendly antifouling coating for ships The coating can be easily washed away with a high-pressure water gun, exposing the complete underlying coating; then, the subsequent matching antifouling coating is applied according to the coating process requirements.

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