Water-based bio-friendly antifouling paint and preparation method thereof

Abstract

The invention discloses a water-based bio-friendly antifouling coating and a preparation method thereof, and the coating comprises the following components in parts by weight: 30-90 parts of a water-based acrylic monomer, 10-30 parts of an initiator, 10-20 parts of an emulsifier, 30-90 parts of water-based epoxy resin, 5-20 parts of capsaicin, 2-5 parts of a coupling agent, 2-5 parts of a catalyst, 5-20 parts of a biological antifouling agent, 0.5-1 part of a thickener and 0.5-1 part of a dispersant. The paint is prepared from the following components in parts by weight: 0.5-1 part of a flatting agent, 0.5-1 part of a defoaming agent, 0.5-1 part of a wetting agent, 0.5-1 part of a flash-rust inhibitor, 5-10 parts of deionized water and 5-10 parts of a solvent. The quick-drying bio-friendly antifouling paint with high mechanical strength is prepared in a manner of combining copolymerization and mechanical stirring. The capsaicin grafted acrylic acid-epoxy resin copolymerized resin provides higher mechanical strength and adhesive force, and the copolymer grafted with capsaicin can achieve double antifouling effects in cooperation with the biological antifouling agent.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of marine and offshore industrial facilities antifouling coatings, in particular to a water-based biologically friendly antifouling coating and a preparation method thereof. BACKGROUND

[0002] With the rapid development of global shipping and offshore engineering, underwater structures and ship surfaces often suffer from the attachment and growth of marine organisms, resulting in biofouling. This phenomenon not only affects the performance and efficiency of equipment, but also increases the cost of maintenance and cleaning, leading to higher energy consumption and emissions. Therefore, it is particularly important to develop effective antifouling technologies. Among the various antifouling methods, antifouling coatings have become the main choice due to their convenient application and long protection period. Traditional antifouling coatings often use toxic ingredients such as copper and biocides, which are effective but pose potential harm to the environment and ecological systems. Therefore, the development of environmentally friendly, low-toxic or non-toxic biologically friendly antifouling coatings has become a hot research topic. These new coatings not only need to have excellent antifouling performance, but also need to consider environmental protection and economic benefits. The progress of related technologies, including the application of new materials (such as natural plant extracts), modified polymers, and innovative coating techniques, is driving the development of antifouling coatings towards more sustainable and efficient directions. SUMMARY

[0003] In view of the deficiencies of the prior art, the present application provides a water-based biologically friendly antifouling coating and a preparation method thereof.

[0004] According to a first aspect of the present application, a water-based biologically friendly antifouling coating is disclosed, comprising the following components in weight percentage:

[0005] Water-based acrylic monomer 30-90 parts, initiator 10-30 parts, emulsifier 10-20 parts, water-based epoxy resin 30-90 parts, capsaicin 5-20 parts, coupling agent 2-5 parts, catalyst 2-5 parts, biological antifouling agent 5-20 parts, thickening agent 0.5-1 part, dispersing agent 0.5-1 part, leveling agent 0.5-1 part, defoaming agent 0.5-1 part, wetting agent 0.5-1 part, anti-flash rust agent 0.5-1 part, deionized water 5-10 parts, solvent 5-10 parts.

[0006] According to an embodiment of the present application, the initiator is one of persulfate salts and azo compounds.

[0007] According to an embodiment of the present application, the coupling agent is one of 3-aminopropyl triethoxysilane and silane coupling agent.

[0008] According to an embodiment of the present application, the catalyst is one of p-toluenesulfonic acid, triethylamine, and 1-methylimidazole.

[0009] According to an embodiment of the present application, the emulsifier is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and polyethylene glycol octylphenyl ether.

[0010] According to an embodiment of the present application, the water-based epoxy resin is one of an anionic water-based epoxy resin, a cationic water-based epoxy resin, or a non-ionic water-based epoxy resin.

[0011] According to an embodiment of the present application, the water-based acrylic pre-emulsification treatment is to mix the water-based acrylic monomer with an appropriate amount of emulsifier and stir at high speed (5000-10000 rpm) to form a stable emulsion.

[0012] According to an embodiment of the present application, the capsaicin is modified using a coupling agent which reacts with the phenolic hydroxyl group of capsaicin; an initiator is used to initiate a free radical polymerization reaction, the double bond in the water-based acrylic acid participates in the polymerization, and the capsaicin is embedded in the structure of the acrylic resin through the action of the coupling agent; the copolymer (capsaicin grafted acrylic resin) is reacted with the epoxy resin, the epoxy group of the epoxy resin is ring-opened under the action of a catalyst, and reacts with the hydroxyl group in the copolymer to form a stable covalent bond.

[0013] According to an embodiment of the present application, the biological antifouling agent is one or more of capsaicin and its derivatives, butenolide, tea polyphenol, and chitosan.

[0014] According to an embodiment of the present application, the thickening agent is one of hydroxyethyl cellulose, BYK-420, Rheolate 278, etc.; the dispersing agent is one of BYK-190, BYK-2225, Disperbyk-2015; the leveling agent is one of BYK-349, TEGOGlide 100; the defoaming agent is one of BYK-033, TEGO Foamex 8050; the wetting agent is one of BYK-377, Dynol 360; the anti-flash rust agent is one of BYK-4510, Cerium Nitrate; and the solvent is one of ethylene glycol butyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

[0015] According to an embodiment of the present application, the above-mentioned additives are added to the synthesized capsaicin grafted acrylic resin-epoxy resin copolymer in multiple times, and are prepared into a water-based biological-friendly antifouling paint through high-speed stirring.

[0016] According to an embodiment of the present application, the water-based biological-friendly antifouling paint is sprayed onto ships and marine industrial facilities by spraying, brushing, rolling, etc.

[0017] Compared with the prior art, the present application has the following excellent effects

[0018] 1. The phenolic hydroxyl group on capsaicin can react with it to obtain the active site for reaction with acrylic resin through the action of coupling agent, and the active epoxy group in silane coupling agent can promote further copolymerization reaction with water-based epoxy resin.

[0019] 2. Capsaicin, as one of the biological antifouling agents, has certain antifouling performance itself, and grafting to the acrylic-epoxy resin molecular chain makes the film-forming resin itself have certain antifouling characteristics. Ultimately, the double antifouling of biological antifouling agent can be realized, greatly enhancing the long-term and economic performance of the coating.

[0020] 3. No toxic antifouling agent such as cuprous oxide is used, and biological antifouling agent and biological antifouling grafting group are used for antifouling, which is more environmentally friendly. DETAILED DESCRIPTION

[0021] The application will be further described in combination with specific implementation.

[0022] Example 1

[0023] Under the conditions of normal temperature and pressure drying, first, 30 parts of water-based acrylic monomer, 10 parts of sodium dodecyl sulfate and 50 parts of deionized water were put into a reaction kettle and pre-emulsified at 5000 rpm; then 5 parts of capsaicin and 2 parts of KH-560 silane coupling agent were surface modified, KH-560 had active epoxy group, which could react with the phenolic hydroxyl group of capsaicin. Through this step, capsaicin obtained the active site for combination with acrylic acid and epoxy resin; then 2 parts of AIBN was used to initiate free radical polymerization reaction, and capsaicin was embedded into the structure of acrylic resin by the action of AIBN; finally, 30 parts of capsaicin grafted acrylic resin, 2 parts of triethylamine and 30 parts of E-44 type water-based epoxy resin were used for copolymerization reaction, thereby preparing capsaicin grafted acrylic resin-epoxy resin copolymer.

[0024] 30 parts of the above prepared capsaicin grafted acrylic resin-epoxy resin copolymer and 20 parts of butenolide were put into a blender and stirred at a speed of 3000 rpm, then BYK-420, BYK-190, BYK-349, BYK-033, Dynol 360 and Cerium Nitrate were added respectively at 0.5 parts during stirring, and the stirring was continued at 3000 rpm for 30 min to obtain water-based antifouling coating. Finally, the antifouling protection can be realized by spraying the coating on the substrate by spraying.

[0025] Example 2

[0026] Under the condition of normal temperature and pressure drying, first, 30 parts of water-based acrylic monomer, 10 parts of sodium dodecyl sulfate and 50 parts of deionized water were put into the reaction kettle and pre-emulsified at 5000 rpm; then 5 parts of capsaicin and 5 parts of KH-560 silane coupling agent were surface modified, KH-560 has active epoxy groups, which can react with the phenolic hydroxyl group of capsaicin. Through this step, capsaicin obtains active sites combined with acrylic acid and epoxy resin; then 5 parts of AIBN is used to initiate free radical polymerization, and capsaicin is embedded in the structure of acrylic resin by the action of AIBN; finally, 30 parts of capsaicin grafted acrylic resin, 5 parts of triethylamine and 30 parts of EPICLON H-502-42W water-based epoxy resin are used for copolymerization, so as to prepare capsaicin grafted acrylic resin-epoxy resin copolymer.

[0027] 30 parts of the above prepared capsaicin grafted acrylic resin-epoxy resin copolymer and 20 parts of butenolide were put into a stirrer and stirred at a speed of 3000 rpm, then BYK-420, BYK-190, BYK-349, BYK-033, Dynol 360, Cerium Nitrate were added respectively 0.5 parts during stirring, and then stirred at 3000 rpm for 30 min to obtain water-based antifouling coating. Finally, the water-based antifouling coating was sprayed on the substrate by spraying to protect against fouling.

[0028] Comparative Example 1

[0029] Under the condition of normal temperature and pressure drying, first, 30 parts of water-based acrylic monomer, 10 parts of sodium dodecyl sulfate and 50 parts of deionized water were put into the reaction kettle and pre-emulsified at 5000 rpm; then 5 parts of capsaicin and 5 parts of KH-560 silane coupling agent were surface modified, KH-560 has active epoxy groups, which can react with the phenolic hydroxyl group of capsaicin. Through this step, capsaicin obtains active sites combined with acrylic acid and epoxy resin; then 5 parts of AIBN is used to initiate free radical polymerization, and capsaicin is embedded in the structure of acrylic resin by the action of AIBN.

[0030] 30 parts of the above prepared capsaicin grafted acrylic resin and 20 parts of butenolide were put into a stirrer and stirred at a speed of 3000 rpm, then BYK-420, BYK-190, BYK-349, BYK-033, Dynol 360, Cerium Nitrate were added respectively 0.5 parts during stirring, and then stirred at 3000 rpm for 30 min to obtain water-based antifouling coating. Finally, the water-based antifouling coating was sprayed on the substrate by spraying to protect against fouling.

[0031] Comparative Example 2

[0032] Under the condition of normal temperature and pressure drying, first, 30 parts of water-based acrylic monomer, 10 parts of sodium dodecyl sulfate and 50 parts of deionized water were put into the reaction kettle and pre-emulsified at 5000 rpm; then 5 parts of capsaicin, 2 parts of KH-560 silane coupling agent were surface modified, KH-560 had active epoxy group, which could react with the phenolic hydroxyl group of capsaicin. Through this step, capsaicin obtained the active site combined with acrylic acid and epoxy resin; then 2 parts of AIBN was used to initiate free radical polymerization, capsaicin was embedded into the structure of acrylic resin by the action of AIBN; finally, 30 parts of capsaicin grafted acrylic resin, 2 parts of triethylamine, 30 parts of E-44 type water-based epoxy resin were used for copolymerization, thus capsaicin grafted acrylic resin-epoxy resin copolymer was prepared.

[0033] 30 parts of the above prepared capsaicin grafted acrylic resin-epoxy resin copolymer and 20 parts of cuprous oxide were put into a blender and stirred at a speed of 3000 rpm, then BYK-420, BYK-190, BYK-349, BYK-033, Dynol 360, Cerium Nitrate were added respectively at 0.5 parts during stirring, and then stirred at 3000 rpm for 30 min to obtain water-based antifouling coating. Finally, the water-based antifouling coating was sprayed onto the substrate by spraying to protect against fouling.

[0034] Table 1 Main performance parameters of various water-based biologically friendly antifouling coatings

[0035]

[0036] Note: The coating hardness refers to the pencil hardness; the adhesion test uses a digital pull-off adhesion tester; the weather resistance uses xenon lamp aging test and outdoor exposure test; the antifouling performance test mainly uses the most common E. coli as the test source. The test is carried out by contacting the bacterial suspension, immersing the sample in the liquid medium containing E. coli, and soaking for 24 hours. After taking out the sample, observe the adhesion of E. coli on the surface of the sample under a microscope, record the number and distribution of the adhesion. If there is less or no bacteria adhered to the surface of the sample, it indicates good antifouling performance.

[0037] From the comparison of the main performance parameters of the above four water-based antifouling coatings, it can be seen that the grafted capsaicin acrylic resin-epoxy resin synergistic biological antifouling agent has better antifouling, anticorrosion and physical properties. This also shows that the effect of double antifouling characteristics is obvious due to one-way antifouling, and the coating does not use toxic antifouling agents such as cuprous oxide, so it has more environmental characteristics.

Claims

1. A water-based bio-friendly antifouling coating and a preparation method thereof, characterized in that: The composition comprises the following components in parts by weight: 30-90 parts of water-based acrylic monomer, 10-30 parts of initiator, 10-20 parts of emulsifier, 30-90 parts of water-based epoxy resin, 5-20 parts of capsaicin, 2-5 parts of coupling agent, 2-5 parts of catalyst, 5-20 parts of biofouling agent, 0.5-1 part of thickener, 0.5-1 part of dispersant, 0.5-1 part of leveling agent, 0.5-1 part of defoaming agent, 0.5-1 part of wetting agent, 0.5-1 part of anti-flash rust agent, 5-10 parts of deionized water, and 5-10 parts of solvent.

2. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The initiator is a persulfate or an azo compound.

3. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The coupling agent is one of 3-aminopropyltriethoxysilane and a silane coupling agent.

4. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The catalyst is one of p-toluenesulfonic acid, triethylamine and 1-methylimidazole.

5. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The emulsifier is one of sodium lauryl sulfate, sodium dodecylbenzene sulfonate, and polyethylene glycol octylphenyl ether.

6. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The waterborne epoxy resin is one of anionic waterborne epoxy resin, cationic waterborne epoxy resin or nonionic waterborne epoxy resin.

7. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: A stable emulsion is formed by mixing an aqueous acrylic monomer with an appropriate amount of emulsifier and stirring at high speed (5000-10000 rpm).

8. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: Capsaicin is modified using a coupling agent, which reacts with the phenolic hydroxyl group of capsaicin; an initiator is used to initiate a free radical polymerization reaction, and the double bonds in the water-based acrylic acid participate in the polymerization. Capsaicin is embedded in the acrylic resin structure through the action of the coupling agent; the above copolymer (capsaicin grafted acrylic resin) is reacted with an epoxy resin, and the epoxy group of the epoxy resin is ring-opened under the action of a catalyst and reacts with the hydroxyl group in the copolymer to form a stable covalent bond.

9. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The biological antifouling agent is one or more of capsaicin and its derivatives, butenolide, tea polyphenols and chitosan.

10. The water-based bio-friendly antifouling coating according to claim 1, characterized in that: The thickener is one of hydroxyethyl cellulose, BYK-420, Rheolate 278, etc.; the dispersant is one of BYK-190, BYK-2225, and Disperbyk-2015; the leveling agent is one of BYK-349 and TEGO Glide 100; the defoaming agent is one of BYK-033 and TEGO Foamex 8050; the wetting agent is one of BYK-377 and Dynol360; the flash rust inhibitor is one of BYK-4510 and Cerium Nitrate; and the solvent is one of ethylene glycol butyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

11. The water-based bio-friendly antifouling coating according to claims 1-9, characterized in that: The auxiliary agent is added into the synthesized capsaicin grafted acrylic resin-epoxy resin copolymer in multiple times, and is prepared into a water-based bio-friendly antifouling coating by high-speed stirring.

12. The water-based bio-friendly antifouling coating according to claim 10, characterized in that: Water-based bio-friendly antifouling coatings are applied to ships and marine industrial facilities by spraying, brushing, roller coating, etc.

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