Underwater anti-drag coating for preventing adhesion of marine organisms as well as preparation and application of underwater anti-drag coating

Abstract

The invention relates to the technical field of ocean engineering materials, and particularly discloses an underwater anti-drag coating for preventing adhesion of marine organisms as well as preparation and application of the underwater anti-drag coating. The coating is composed of special fluorosilicone resin, super-amphiphobic nanoparticles, fluorine-containing silicone oil sustained-release microcapsules, a dispersing agent, a defoaming agent and a curing agent, the special fluorosilicone resin, the super-amphiphobic nanoparticles, the fluorine-containing silicone oil sustained-release microcapsules, the dispersing agent and the defoaming agent are subjected to high-speed dispersion in proportion to prepare matrix resin, and then the matrix resin and the curing agent are subjected to coating mixing. And finally, constructing and curing. Performance tests show that the biological adhesion area of the coating within 180 days is lower than 4%, the barnacle adhesion density is smaller than 300 barnacles / m < 2 >, the resistance reduction rate is 20-26%, the contact angle is 107-112 degrees, the sliding angle is 14-17 degrees, the coating has no abnormity after being soaked in seawater for 3600 hours, and the contact angle is kept 130 degrees or above after TABER friction. The coating has high-efficiency biological adhesion prevention, lasting resistance reduction and seawater corrosion resistance, is suitable for ships, marine equipment and the like, can reduce energy consumption, and has remarkable economic and ecological values.

Description

Technical Field

[0001] The invention belongs to the technical field of marine engineering materials and discloses an underwater drag-reducing coating for preventing marine organism attachment and the preparation and application thereof. Background Art

[0002] In the field of marine engineering, ships, underwater vehicles and marine facilities are exposed to complex water environments for a long time and face two core challenges: marine organism attachment and underwater movement resistance, both of which directly affect equipment operating efficiency, energy consumption and maintenance costs.

[0003] Marine biofouling increases the roughness of a ship's hull surface, damaging the appearance of the equipment and significantly increasing water resistance. Data shows that if even 10% of marine biofouling adheres to a ship's surface, fuel consumption will increase by 15-20%. Annually, biofouling causes the global shipping industry to incur excess energy losses exceeding tens of billions of dollars. Traditional antifouling methods rely on heavy metal coatings containing copper and tin. While these can inhibit biofouling, they contribute to heavy metal pollution in the ocean, disrupting the ecological balance and leading to their gradual use restrictions by the International Maritime Organization. Furthermore, underwater resistance is a key factor limiting ship speed increases and energy efficiency optimization. Conventional hull coatings have high surface energy, which can easily create turbulence at the contact surface, increasing frictional resistance. Research has shown that reducing underwater resistance by 10% can increase a ship's endurance by 8-12%, offering significant economic and tactical benefits for large commercial vessels and underwater vehicles.

[0004] Existing technologies have significant limitations: While physical antifouling coatings, including epoxy coatings, offer some corrosion resistance, their surface structures struggle to form an effective barrier, allowing barnacle larvae to attach at densities exceeding 2,000 per square meter. Conventional drag-reducing coatings often rely on a single low-surface-energy material. While they can provide short-term drag reduction, they lack long-term biofouling resistance. After six months of use, biofouling often exceeds 30%, requiring frequent maintenance. Furthermore, some coatings utilize solvent-based systems, which require long curing times and insufficient resistance to seawater erosion, making them inadequate for long-term underwater operations.

[0005] Therefore, the development of an environmentally friendly coating that has both high-efficiency anti-marine biofouling and long-lasting underwater drag reduction functions has become an urgent need in the field of marine engineering materials. Summary of the Invention

[0006] In order to overcome the above-mentioned defects of the prior art, the present invention provides an underwater drag-reducing coating that prevents the attachment of marine organisms, as well as its preparation and application. By synergistically compounding special fluorosilicone resin, super-amphiphobic nanoparticles and fluorine-containing silicone oil sustained-release microcapsules, combined with a specific preparation process, the present invention solves the problems of weak anti-biological attachment ability, poor drag reduction effect, insufficient durability and environmental pollution of existing coatings.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] An underwater drag-reducing coating for preventing marine organisms from adhering comprises the following raw materials: special fluorosilicone resin, super-amphiphobic nanoparticles, fluorosilicone oil slow-release microcapsules, a dispersant, a defoaming agent and a curing agent.

[0009] Preferably, the special fluorosilicone resin is purchased from Shenzhen Weijing High-tech Materials Technology Co., Ltd., model WJ-FS-01, with a solid content of 60% and a hydroxyl value of 3.5%.

[0010] Preferably, the super-amphiphobic nanoparticles are silica-based and purchased from Nanjing Hitech Nanomaterials Co., Ltd., with a particle size of 50-100 nm and a hydrophobic angle of ≥150°.

[0011] Preferably, the fluorinated silicone oil sustained-release microcapsules are purchased from Shanghai Runhe Nanotechnology Co., Ltd., with a shell material of polyurethane and a core material of fluorinated silicone oil, and a particle size of 5-10 μm.

[0012] Preferably, the dispersant is BYK-110 (polycarboxylate) and the defoamer is BYK-024 (silicone), both purchased from BYK-Chemie, Germany.

[0013] Preferably, the curing agent is HDI trimer, purchased from Bayer, Germany, model N3390, with an NCO content of 21%.

[0014] Preferably, the mass ratio of each raw material is: 600-780 parts of special fluorosilicone resin, 110-200 parts of super amphiphobic nanoparticles, 60-100 parts of fluorine-containing silicone oil sustained-release microcapsules, 12-30 parts of dispersant, 8-20 parts of defoaming agent, and the amount of curing agent added is 1 / 5 of the mass of the main resin.

[0015] Preferably, the method for preparing the underwater drag-reducing coating for preventing marine organism attachment comprises the following steps:

[0016] (1) Preparation of main resin: Weigh special fluorosilicone resin and add it to a stirring kettle, stir it at 800-1500 r / min for 10-20 min, weigh super-amphiphobic nanoparticles and slowly add them to the stirring kettle, keep stirring at the same speed for 10-20 min, then weigh fluorosilicone oil microcapsules and add them to the stirring kettle, stir at the same speed for 10-20 min, finally weigh dispersant and defoamer and add them to the stirring kettle, increase the speed to 1200-1500 r / min and stir for 20 min to obtain a uniform main resin, which is then sealed for later use;

[0017] (2) Coating mixing: Weigh the above-mentioned main resin and curing agent, pour them into a stirring kettle at a mass ratio of 5:1, stir with an electric stirrer at 500 r / min for 5-8 minutes, and then let it stand for 2 minutes to defoam;

[0018] (3) Construction and curing: Use a wet film preparation device to coat on a tinplate standard plate, control the dry film thickness to 50-100 μm, place in an environment of 25°C and 60% relative humidity, and allow the surface to dry for 1 hour and the actual drying for 120 hours.

[0019] In summary, the present invention has the following effects:

[0020] 1. Excellent anti-biological adhesion performance: The synergistic effect of the micro-nano rough structure constructed by super-amphiphobic nanoparticles and the fluorinated silicone oil sustained-release microcapsules forms a dual protection of physical barrier and chemical inhibition, greatly reducing the problem of increased surface roughness caused by biological adhesion.

[0021] 2. Significant and long-lasting drag reduction effect: The low surface energy characteristics of special fluorosilicone resin combined with the hydrophobic structure of super-amphiphobic nanoparticles can effectively reduce turbulent friction of water flow, with excellent surface performance stability and long-term use without loss of effectiveness.

[0022] 3. Strong resistance to seawater erosion: The use of special fluorosilicone resin and HDI trimer curing agent to form a cross-linked network, combined with the barrier effect of microcapsules, can meet the needs of long-term underwater operations and reduce frequent maintenance costs.

[0023] 4. Outstanding environmental protection: Abandoning the traditional heavy metal antifouling ingredients containing copper and tin, it adopts fluorinated silicone oil microcapsule sustained-release technology, without the release of heavy metal ions, in line with the environmental protection requirements of the International Maritime Organization, avoiding marine ecological pollution, and solving the environmental hazards of traditional antifouling coatings.

[0024] 5. Wide range of applications: It can be widely used on the surface of ships, underwater vehicles, offshore drilling platforms and other marine equipment. It can adapt to static immersion environments and withstand dynamic water flow impacts. It has multiple functions of anti-fouling, drag reduction and anti-corrosion, and has significant comprehensive economic benefits. DETAILED DESCRIPTION

[0025] In the embodiments of the present invention, special fluorosilicone resin was purchased from Shenzhen Weijing High-tech Materials Technology Co., Ltd., model WJ-FS-01; super-amphiphobic nanoparticles were purchased from Nanjing Hitech Nanomaterials Co., Ltd., with a particle size of 50-100 nm; fluorinated silicone oil sustained-release microcapsules were purchased from Shanghai Runhe Nanotechnology Co., Ltd., with a shell material of polyurethane and a core material of fluorinated silicone oil, with a particle size of 5-10 μm; dispersant BYK-110 and defoamer BYK-024 were purchased from BYK Chemicals of Germany; and curing agent HDI trimer was purchased from Bayer of Germany, model N3390.

[0026] Example 1

[0027] Example 1 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment.

[0028] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0029] 1. Preparation of the main resin: Add 600g of special fluorosilicone resin to a stirring kettle, set the speed to 800r / min, and stir for 10min. Take 200g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 800r / min for 15min. Then add 100g of fluorine-containing silicone oil microcapsules and continue stirring at 800r / min for 15min. Finally, add 30g of dispersant and 20g of defoamer to the stirring kettle in sequence, adjust the speed to 1200r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0030] 2. Coating mixing: Weigh 800g of the above-mentioned main resin, add 160g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 5min, mix well and let it stand for 2min to defoam.

[0031] 3. Construction and curing: Use a wet film preparation device to coat on a 100mm×100mm tinplate standard plate, control the dry film thickness to 50μm, place it in an environment of 25℃ and relative humidity of 60%, dry it for 1 hour, and it should not be sticky to the touch. Dry it for 120 hours and wait for it to be completely cured.

[0032] Example 2

[0033] Example 2 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0034] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0035] 1. Preparation of the main resin: Add 620g of special fluorosilicone resin to a stirring kettle, set the speed to 850r / min, and stir for 10min. Take 190g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 850r / min for 15min. Then add 90g of fluorine-containing silicone oil microcapsules and continue stirring at 850r / min for 15min. Finally, add 28g of dispersant and 18g of defoamer to the stirring kettle in sequence, adjust the speed to 1250r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0036] 2. Coating mixing: Weigh 810g of the above-mentioned main resin, add 162g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 6min, mix well and let it stand for 2min to defoam.

[0037] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 60 μm, and the curing conditions are the same as in Example 1.

[0038] Example 3

[0039] Example 3 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0040] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0041] 1. Preparation of the main resin: Add 650g of special fluorosilicone resin to a stirring kettle, set the speed to 900r / min, and stir for 10min. Take 180g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 900r / min for 15min. Then add 80g of fluorine-containing silicone oil microcapsules and continue stirring at 900r / min for 15min. Finally, add 25g of dispersant and 15g of defoamer to the stirring kettle in sequence, adjust the speed to 1300r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0042] 2. Coating mixing: Weigh 850g of the above-mentioned main resin, add 170g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 7min, mix evenly and let it stand for 2min to defoam.

[0043] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 70 μm, and the curing conditions are the same as in Example 1.

[0044] Example 4

[0045] Example 4 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment.

[0046] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0047] 1. Preparation of the main resin: Add 680g of special fluorosilicone resin to a stirring kettle, set the speed to 900r / min, and stir for 10min. Take 170g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 900r / min for 15min. Then add 70g of fluorine-containing silicone oil microcapsules and continue stirring at 900r / min for 15min. Finally, add 22g of dispersant and 12g of defoamer to the stirring kettle in sequence, adjust the speed to 1350r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0048] 2. Coating mixing: Weigh 870g of the above-mentioned main resin, add 174g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 8min, mix well and let it stand for 2min to defoam.

[0049] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 80 μm, and the curing conditions are the same as in Example 1.

[0050] Example 5

[0051] Example 5 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0052] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0053] 1. Preparation of the main resin: Add 700g of special fluorosilicone resin to a stirring kettle, set the speed to 950r / min, and stir for 10min. Take 150g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 950r / min for 15min. Then add 80g of fluorosilicone oil microcapsules and continue stirring at 950r / min for 15min. Finally, add 20g of dispersant and 15g of defoamer to the stirring kettle in sequence, adjust the speed to 1400r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0054] 2. Coating mixing: Weigh 875g of the above-mentioned main resin, add 175g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 6min, mix well and let it stand for 2min to defoam.

[0055] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 90 μm, and the curing conditions are the same as in Example 1.

[0056] Example 6

[0057] Example 6 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0058] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0059] 1. Preparation of the main resin: Add 720g of special fluorosilicone resin to a stirring kettle, set the speed to 950r / min, and stir for 10min. Take 140g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 950r / min for 15min. Then add 70g of fluorinated silicone oil microcapsules and continue stirring at 950r / min for 15min. Finally, add 18g of dispersant and 12g of defoamer to the stirring kettle in sequence, adjust the speed to 1400r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0060] 2. Coating mixing: Weigh 885g of the above-mentioned main resin, add 177g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 7min, mix well and let it stand for 2min to defoam.

[0061] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to be 100 μm, and the curing conditions are the same as those in Example 1.

[0062] Example 7

[0063] Example 7 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0064] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0065] 1. Preparation of the main resin: Add 750g of special fluorosilicone resin to a stirring kettle, set the speed to 1000r / min, and stir for 10min. Take 120g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 1000r / min for 15min. Then add 60g of fluorosilicone oil microcapsules and continue stirring at 1000r / min for 15min. Finally, add 15g of dispersant and 10g of defoamer to the stirring kettle in sequence, adjust the speed to 1500r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0066] 2. Coating mixing: Weigh 885g of the above-mentioned main resin, add 177g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 8min, mix well and let it stand for 2min to defoam.

[0067] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 50 μm, and the curing conditions are the same as in Example 1.

[0068] Example 8

[0069] Example 8 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0070] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0071] 1. Preparation of the main resin: Add 780g of special fluorosilicone resin to a stirring kettle, set the speed to 1000r / min, and stir for 10min. Take 110g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 1000r / min for 15min. Then add 60g of fluorosilicone oil microcapsules and continue stirring at 1000r / min for 15min. Finally, add 12g of dispersant and 8g of defoamer to the stirring kettle in sequence, adjust the speed to 1500r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0072] 2. Coating mixing: Weigh 900g of the above-mentioned main resin, add 180g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 5min, mix well and let it stand for 2min to defoam.

[0073] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 60 μm, and the curing conditions are the same as in Example 1.

[0074] Example 9

[0075] Example 9 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0076] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0077] 1. Preparation of the main resin: Add 600g of special fluorosilicone resin to a stirring kettle, set the speed to 850r / min, and stir for 10min. Take 180g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 850r / min for 15min. Then add 100g of fluorine-containing silicone oil microcapsules and continue stirring at 850r / min for 15min. Finally, add 25g of dispersant and 15g of defoamer to the stirring kettle in sequence, adjust the speed to 1300r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0078] 2. Coating mixing: Weigh 830g of the above-mentioned main resin, add 166g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 6min, mix well and let it stand for 2min to defoam.

[0079] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 70 μm, and the curing conditions are the same as in Example 1.

[0080] Example 10

[0081] Example 10 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment.

[0082] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0083] 1. Preparation of the main resin: Add 650g of special fluorosilicone resin to a stirring kettle, set the speed to 900r / min, and stir for 10min. Take 160g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 900r / min for 15min. Then add 80g of fluorosilicone oil microcapsules and continue stirring at 900r / min for 15min. Finally, add 22g of dispersant and 12g of defoamer to the stirring kettle in sequence, adjust the speed to 1400r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0084] 2. Coating mixing: Weigh 855g of the above-mentioned main resin, add 171g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 7min, mix well and let it stand for 2min to defoam.

[0085] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 80 μm, and the curing conditions are the same as in Example 1.

[0086] Example 11

[0087] Example 11 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0088] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0089] 1. Preparation of the main resin: Add 700g of special fluorosilicone resin to a stirring kettle, set the speed to 950r / min, and stir for 10min. Take 140g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 950r / min for 15min. Then add 80g of fluorinated silicone oil microcapsules and continue stirring at 950r / min for 15min. Finally, add 20g of dispersant and 10g of defoamer to the stirring kettle in sequence, adjust the speed to 1400r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0090] 2. Coating mixing: Weigh 865g of the above-mentioned main resin, add 173g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 8min, mix well and let it stand for 2min to defoam.

[0091] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 90 μm, and the curing conditions are the same as in Example 1.

[0092] Example 12

[0093] Example 12 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment.

[0094] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0095] 1. Preparation of the main resin: Add 730g of special fluorosilicone resin to a stirring kettle, set the speed to 950r / min, and stir for 10min. Take 130g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 950r / min for 15min. Then add 70g of fluorosilicone oil microcapsules and continue stirring at 950r / min for 15min. Finally, add 16g of dispersant and 10g of defoamer to the stirring kettle in sequence, adjust the speed to 1400r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0096] 2. Coating mixing: Weigh 865g of the above-mentioned main resin, add 173g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 5min, mix well and let it stand for 2min to defoam.

[0097] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to be 100 μm, and the curing conditions are the same as those in Example 1.

[0098] Example 13

[0099] Example 13 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment.

[0100] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0101] 1. Preparation of the main resin: Add 760g of special fluorosilicone resin to a stirring kettle, set the speed to 1000r / min, and stir for 10min. Take 120g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 1000r / min for 15min. Then add 60g of fluorosilicone oil microcapsules and continue stirring at 1000r / min for 15min. Finally, add 13g of dispersant and 7g of defoamer to the stirring kettle in sequence, adjust the speed to 1500r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0102] 2. Coating mixing: Weigh 875g of the above-mentioned main resin, add 175g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 6min, mix well and let it stand for 2min to defoam.

[0103] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 50 μm, and the curing conditions are the same as in Example 1.

[0104] Example 14

[0105] Example 14 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment.

[0106] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0107] 1. Preparation of the main resin: Add 630g of special fluorosilicone resin to a stirring kettle, set the speed to 850r / min, and stir for 10min. Take 190g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 850r / min for 15min. Then add 90g of fluorinated silicone oil microcapsules and continue stirring at 850r / min for 15min. Finally, add 27g of dispersant and 17g of defoamer to the stirring kettle in sequence, adjust the speed to 1300r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0108] 2. Coating mixing: Weigh 835g of the above-mentioned main resin, add 167g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 7min, mix well and let it stand for 2min to defoam.

[0109] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 60 μm, and the curing conditions are the same as in Example 1.

[0110] Example 15

[0111] Example 15 provides a method for preparing an underwater drag-reducing coating that prevents marine organisms from adhering.

[0112] The preparation method of an underwater drag-reducing coating for preventing marine organism attachment in this embodiment is specifically as follows.

[0113] 1. Preparation of the main resin: Add 670g of special fluorosilicone resin to a stirring kettle, set the speed to 900r / min, and stir for 10min. Take 170g of super-amphiphobic nanoparticles and slowly add them to the stirring kettle. Keep stirring at 900r / min for 15min. Then add 90g of fluorinated silicone oil microcapsules and continue stirring at 850r / min for 15min. Finally, add 23g of dispersant and 13g of defoamer to the stirring kettle in sequence, adjust the speed to 1400r / min, and stir for 20min to obtain a uniform main resin. Seal it for later use.

[0114] 2. Coating mixing: Weigh 855g of the above-mentioned main resin, add 171g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 8min, mix well and let it stand for 2min to defoam.

[0115] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 70 μm, and the curing conditions are the same as in Example 1.

[0116] Comparative Example 1

[0117] Comparative Example 1 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment. The specific preparation method is as follows.

[0118] 1. Preparation of the main resin: 700 g of a special fluorosilicone resin without nanoparticles was added to a stirred tank, followed by 200 g of microcapsules. Finally, 20 g of a dispersant and 15 g of a defoamer were added to the stirred tank in sequence to obtain a uniform main resin. The mixture was sealed and used for further processing. The remaining process was the same as in Example 5.

[0119] 2. Mixing: Weigh 850g of the above-mentioned main resin, add 170g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 6min, mix well and let it stand for 2min to defoam.

[0120] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 70 μm, and the curing conditions are the same as in Example 1.

[0121] Comparative Example 2

[0122] Comparative Example 2 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment. The specific preparation method is as follows.

[0123] 1. Preparation of the main resin: 700 g of a special fluorosilicone resin was added to a stirred tank, followed by 200 g of the non-empty microcapsule nanoparticles. Finally, 20 g of a dispersant and 15 g of a defoamer were added to the stirred tank in sequence to obtain a uniform main resin. The mixture was sealed and used for standby. The remaining process conditions were the same as in Example 5.

[0124] 2. Mixing: Weigh 850g of the above-mentioned main resin, add 170g of curing agent, pour into a stirring kettle, stir with an electric stirrer at 500r / min for 6min, mix well and let it stand for 2min to defoam.

[0125] 3. Construction and curing: Use a wet film preparation device to coat on a 100 mm × 100 mm tinplate standard plate, control the dry film thickness to 70 μm, and the curing conditions are the same as in Example 1.

[0126] Comparative Example 3

[0127] Comparative Example 3 provides a method for preparing an underwater drag-reducing coating that prevents marine organism attachment. The specific preparation method is as follows.

[0128] In Comparative Example 3, a commercially available epoxy coating was used, including 1000 g of E-44 epoxy resin and 100 g of ethylenediamine. The coating was stirred at 500 r / min for 10 min, with a dry film thickness of 70 μm, and cured at 25° C. for 7 days.

[0129] Performance Testing

[0130] A JC2000D contact angle meter was used, with 5 μL of distilled water as the test medium. Five parallel tests were performed and the average values ​​were taken to measure the contact angle and sliding angle values. The larger the contact angle and the smaller the sliding angle, the better the hydrophobicity of the coating surface, which is conducive to drag reduction and prevention of biological attachment. The TABER friction test evaluated the wear resistance and surface performance stability of the coating by the change in contact angle after friction. The less the contact angle decreases after friction, the more stable the performance. The seawater corrosion resistance was evaluated by immersing the coating in a 3.5% NaCl solution for 3600 hours in accordance with the GB / T1771-2007 standard. The coating was observed for bubbling and shedding to determine its seawater corrosion resistance. The 180-day biological attachment area was evaluated by immersing the coating sample in a natural seawater environment for 180 days. The proportion of biological attachment area was calculated. The lower the proportion, the better the long-term anti-biological attachment performance. The resistance reduction rate was calculated by comparing the resistance of the uncoated surface through a circulating water tunnel test. The higher the value, the more significant the drag reduction effect. The following is a summary of the performance test results of Examples 1-15 and Comparative Examples 1-3, as shown in Table 1 below;

[0131] Table 1 Test results of Examples 1-15 and Comparative Examples 1-3

[0132]

[0133] Combined with the performance test results in Table 1, it can be seen that in the test results of Comparative Example 1, the biological attachment area after 180 days is 35%, and the barnacle attachment density exceeds 800 / m 2 , the resistance reduction rate is 8%, the contact angle is 90°, the sliding angle is 25°, the contact angle after TABER friction is 95°, and slight bubbling occurs after 3600h seawater immersion; the results of comparative example 2 are 20% of the biological attachment area after 180 days, and the barnacle attachment density exceeds 600 / m 2 , resistance reduction rate 15%, contact angle 100°, sliding angle 20°, contact angle 105° after TABER friction, no abnormality after 3600h seawater immersion; the results of comparative example 3 are: 180 days biological attachment area 80%, barnacle attachment density exceeds 2000 / m 2, resistance reduction rate ≤ 5%, contact angle 75°, sliding angle 30°, contact angle 60° after TABER friction, and obvious shedding after 3600h seawater immersion; in the performance test results of Examples 1-15, the biological attachment area after 180 days was less than 4%, and the barnacle attachment density was less than 300 / m 2 The resistance reduction rate is between 20%-26%, the contact angle is mostly between 107°-112°, and the sliding angle is 14°-17°; after TABER friction, the contact angle remains above 130°, and there are no abnormalities after 3600h of seawater immersion.

[0134] In summary, the embodiment achieves the unity of efficient anti-biological adhesion, excellent drag reduction performance and long-term durability through the synergistic effect of special fluorosilicone resin, super-amphiphobic nanoparticles and fluorosilicone oil sustained-release microcapsules, while the comparative example lags behind in performance due to the lack of key components or the use of traditional formulas, which verifies the scientific and advanced nature of the formula design of the present invention. At the same time, the trace quaternary ammonium salt groups remaining in the curing agent block the chemical sensing receptors of barnacle larvae through penetration, delaying the biofilm formation cycle to more than 18 months, compared to only 6 months for traditional coatings. The present invention can inhibit the growth of fouling communities from the source, and also has a self-cleaning function. When dirt and impurities adhere to the coating surface, the surface dirt can be washed away by water flow, keeping the coating surface clean, reducing the increase in resistance caused by dirt accumulation, and reducing maintenance costs.

[0135] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. An underwater drag-reducing coating for preventing marine organism attachment, characterized in that: It is made of the following raw materials: special fluorosilicone resin, super-amphiphobic nanoparticles, fluorosilicone oil sustained-release microcapsules, dispersant, defoaming agent and curing agent; The special fluorosilicone resin has a solid content of 60% and a hydroxyl value of 3.5%; the super-amphiphobic nanoparticles are based on silica, have a particle size of 50-100 nm, and a hydrophobic angle of ≥150°; the shell material of the fluorosilicone oil sustained-release microcapsule is polyurethane, the core material is fluorosilicone oil, has a viscosity of 500 cSt, and a particle size of 5-10 μm; the dispersant is a polycarboxylate, the defoaming agent is an organosilicon, and the curing agent is HDI trimer with an NCO content of 21%.

2. The underwater drag-reducing coating for preventing marine biofouling according to claim 1, characterized in that: The raw materials are as follows: 600-780 parts by weight of special fluorosilicone resin, 110-200 parts by weight of super-amphiphobic nanoparticles, 60-100 parts by weight of fluorine-containing silicone oil sustained-release microcapsules, 12-30 parts by weight of dispersant, 8-20 parts by weight of defoamer, and 20% by weight of curing agent based on the weight of the main resin.

3. The underwater drag-reducing coating for preventing marine biofouling according to claim 1, characterized in that: The super-amphiphobic nanoparticles and the fluorine-containing silicone oil sustained-release microcapsules are uniformly dispersed in a main resin formed by a special fluorine silicone resin.

4. A method for preparing an underwater drag-reducing coating for preventing marine biofouling, according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) Preparation of main resin: Weigh special fluorosilicone resin and add it to a stirring kettle, stir it at 800-1500 r / min for 10-20 min, weigh super-amphiphobic nanoparticles and slowly add them to the stirring kettle, keep stirring at the same speed for 10-20 min, then weigh fluorosilicone oil microcapsules and add them to the stirring kettle, stir at the same speed for 10-20 min, finally weigh dispersant and defoamer and add them to the stirring kettle, increase the speed to 1200-1500 r / min and stir for 20 min to obtain a uniform main resin, which is then sealed for later use; (2) Coating mixing: Weigh the above-mentioned main resin and curing agent, pour them into a stirring kettle at a mass ratio of 5:1, stir with an electric stirrer at 500 r / min for 5-8 minutes, and then let it stand for 2 minutes to defoam; (3) Construction and curing: Use a wet film preparation device to coat on a tinplate standard plate, control the dry film thickness to 50-100 μm, place in an environment of 25°C and 60% relative humidity, and allow the surface to dry for 1 hour and the actual drying for 120 hours.

5. The method for preparing an underwater drag-reducing coating for preventing marine biofouling according to claim 4, characterized in that: During the preparation of the main resin, after each stirring is completed, the uniformity of the material dispersion needs to be observed, and it is qualified if there is no obvious agglomerate.

6. The method for preparing an underwater drag-reducing coating for preventing marine biofouling according to claim 4, characterized in that: During the preparation of the main resin, the stirring speed is 800-1500 r / min, and the stirring time each time is 10-20 minutes.

7. Application of an underwater drag-reducing coating for preventing marine organism attachment, characterized in that: The use of an underwater drag-reducing coating against marine biofouling according to any one of claims 1 to 3 in marine equipment, surface biofouling of ships and underwater drag reduction.

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