Self-polishing surface antifouling coating and preparation method and application thereof

Abstract

The present invention discloses a self-polishing surface antifouling coating and a preparation method and application thereof, comprising the following steps: a. grinding super-hydrophobic low-surface-energy silica aerogel into aerogel micropowder particles by ball milling, wherein the particle size of the micropowder particles is less than 80 μm; b. mixing and stirring the aerogel micropowder particles obtained in step a and the self-polishing antifouling paint to form a coating; c. spraying the coating obtained in step b in multiple layers in batches to form a self-polishing surface antifouling paint layer, and the self-polishing surface antifouling paint layer is coated on a steel plate layer. In the above manner, the silica aerogel self-polishing surface antifouling coating of the present invention and its preparation method and application can have excellent anti-marine organism (barnacles, oysters, seaweed and seaweed, etc.) adhesion performance, good anti-corrosion and anti-fouling performance, and can keep the antifouling paint surface of marine engineering equipment and ships free of marine organisms during the service life of the antifouling coating, and the antifouling paint surface is smooth and clean, and the steel structure surface is free of rust.

Description

Technical Field

[0001] The invention relates to the field of coatings, in particular to a self-polishing surface antifouling coating and a preparation method and application thereof. Background Art

[0002] Marine biofouling is the adhesion and growth of marine microorganisms, animals and plants on the surface of marine facilities, which has a profound adverse impact on marine industry and marine activities.

[0003] Marine pollution can increase the ship's navigation resistance by up to 40%, increase the ship's weight, increase fuel consumption, and increase operation and maintenance costs; marine pollution can affect the ship's speed, acoustic detection, block water pipes, and increase propeller noise; marine pollution can block nuclear power plant seawater pipelines, reduce heat exchange efficiency, and cause nuclear accidents; marine pollution can reduce the mesh size of seawater cages, and lack of oxygen in the cages can lead to large-scale deaths of fish and shrimp; marine pollution can hinder the operation of generators in tidal power generation and seawater pumping power storage power stations.

[0004] In the application of foreign antifouling coating technology, antifouling agent-releasing antifouling coatings dominate the market, and Wuxi self-polishing antifouling paint has become the leading antifouling product for ocean-going and deep-sea ships; controlled dissolution antifouling coatings, as a market supplement to Wuxi self-polishing antifouling paint, are mainly used in the coating protection of offshore ships; low surface energy antifouling coatings have entered the market. With the continuous development and maturity of its technology and people's increasing attention to issues such as environmental protection and energy consumption, its market application has shown a trend of continuous expansion.

[0005] After nearly 30 years of development, hydration type, hydrolysis type and mixed type Wuxi self-polishing antifouling paint have been applied to the market, and their antifouling period is 3 years, 5 years and 3-5 years respectively. Major multinational companies have a series of Wuxi self-polishing antifouling paint products to meet the antifouling protection of various ocean-going ships. However, for naval ships, due to their low carrying rate and long berthing time, marine organisms are more likely to attach when they are berthed in the port. The antifouling agent release rate of general Wuxi self-polishing antifouling paint cannot meet the antifouling requirements.

[0006] With the arrival of the complete ban on the use of organotin self-polishing antifouling coatings in 2008 and the growing global call for environmental protection, the development of high-efficiency, non-toxic or low-toxic and environmentally friendly antifouling coatings has a promising future. Among them, low surface energy antifouling coatings are one of the most attractive options.

[0007] Experiments have found that when the coating is in contact with seawater at a temperature >98°C, that is, the surface energy is <25 mJ / m 2 The coating surface has an antifouling effect only when the surface energy is 30-35 mJ / m. However, due to the complexity and diversity of marine organisms, it is impossible for the same coating to meet different surface energy requirements at the same time. For example, the surface energy of barnacles is 30-35 mJ / m. 2The surface is most likely to adhere to moss, and the surface energy of moss is 10-30 mJ / m 2 The surface of the sea is most likely to adhere, and simple low surface energy coatings often only make marine organisms adhere loosely, requiring regular cleaning. In addition, once the attached organisms grow up, they will be difficult to remove, and the paint film is easily damaged during the cleaning process. This has led to a long period of research on low surface energy antifouling coatings. Summary of the invention

[0008] The main technical problem solved by the present invention is to provide a self-polishing surface antifouling coating and a preparation method and application thereof, which can have excellent anti-biological adhesion performance, good anti-corrosion and anti-fouling performance, and can keep the paint surface smooth.

[0009] In order to solve the above technical problems, a technical solution adopted by the present invention is: providing a self-polishing surface antifouling coating, comprising hydrophobic silica aerogel in the form of nano-powder and self-polishing antifouling paint, wherein the silica aerogel powder and the self-polishing antifouling paint are evenly mixed, so that the silica aerogel nano-powder is dispersed in the self-polishing antifouling paint, and the surface of the silica aerogel nano-powder dispersed in the self-polishing antifouling paint is rich in methyl groups, thereby forming a microscopic super-hydrophobic low-surface-energy methyl protective film on the surface of the coating after curing; the sodium hydroxide molecules of the self-polishing antifouling paint are present in the nano-microporous frame of the silica molecules, thereby forming a strongly alkaline surface in the microscopic region.

[0010] In a preferred embodiment of the present invention, the particle size of the nano-powder of the silica aerogel is less than 80 μm.

[0011] In a preferred embodiment of the present invention, the silica molecules in the silica aerogel are combined by van der Waals molecular forces to form a breakable nano-microporous frame, which is peeled off at the molecular nanoscale on the surface of the material to self-polish the surface of the material.

[0012] In a preferred embodiment of the present invention, the pH value of the strongly alkaline surface of the microscopic region is greater than the pH value of the weakly alkaline seawater.

[0013] In a preferred embodiment of the present invention, the self-polishing antifouling paint comprises the following substances in percentage by mass: 15%-24% of xylene, 4%-8% of chloroether resin or polyamide resin or acrylic resin, 1%-5% of n-butanol, 8%-15% of rosin, 5%-10% of zinc oxide, 30%-40% of cuprous oxide, 4%-8% of SEA-NINE211, nano-powdered silica aerogel content of 0.2%~15%, and nano-powdered silica aerogel content of 0.2%~15%.

[0014] In a preferred embodiment of the present invention, the polymer group chain of the chloroether resin, polyamide resin or acrylic resin is partially interrupted by silica aerogel powder, so that the polymer group of the chloroether resin, polyamide resin or acrylic resin is easier to release.

[0015] In order to solve the above technical problems, another technical solution adopted by the present invention is: to provide a method for preparing the above polished surface antifouling coating, comprising the following steps: a. grinding the super-hydrophobic low surface energy silica aerogel into aerogel micro-powder particles by ball milling, wherein the particle size of the micro-powder particles is less than 80 μm; b. mixing the aerogel micro-powder particles obtained in step a with the self-polishing antifouling paint to form a coating; c. spraying the coating obtained in step b in multiple layers in batches to form a coating.

[0016] In a preferred embodiment of the present invention, the coating thickness in step c is 200-400 μm.

[0017] In a preferred embodiment of the present invention, the coating thickness of each spraying in step c is 50-150 microns.

[0018] In order to solve the above technical problems, another technical solution adopted by the present invention is: to provide an application of the above self-polishing surface antifouling coating, wherein the self-polishing surface antifouling coating is coated to form a self-polishing surface antifouling paint layer, wherein the self-polishing surface antifouling paint layer is located on the surface of the connecting and reinforcing paint layer, wherein the connecting and reinforcing paint layer is located on the surface of the primer antirust paint layer, and the primer antirust paint layer is located on the surface of the steel plate layer.

[0019] The beneficial effects of the present invention are as follows: the self-polishing surface antifouling coating of the present invention and its preparation method and application contain super-hydrophobic low-surface-energy aerogel, so that the surface of the antifouling material has microscopic super-hydrophobic properties, preventing the viscous hydrophilic protein fluid secreted by marine organisms from solidifying and bonding on the microscopic super-hydrophobic low-surface-energy methyl groups. Under the shaking of the water flow, the viscous hydrophilic protein fluid secreted by the marine organisms automatically slides on the surface of the methyl protective film, thereby avoiding the attachment of the marine organisms.

[0020] The self-polishing surface antifouling coating of the present invention and its preparation method and application, sodium hydroxide NaOH exists in the nano-microporous frame composed of silicon dioxide molecules, so that the aerogel self-polishing surface antifouling material is microscopically strongly alkaline, and its pH value is much greater than the weakly alkaline seawater, which prevents the roots of seaweed algae from attaching and growing on the microscopic strongly alkaline surface, and the seaweed algae automatically drifts away under the shaking of the water flow.

[0021] The self-polishing surface antifouling coating of the present invention and its preparation method and application have very small molecular binding force between silicon dioxide molecules, and the nano-microporous structure of silicon dioxide molecules bound by van der Waals molecular force is easy to break, so that a small part of the polymer group chain of the chloroether resin is partially separated by the aerogel micropowder, making the polymer group of the chloroether resin easier to release, thereby strengthening the self-polishing slow-release performance of the resin in the antifouling material. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work, among which:

[0023] Figure 1 is a microscopic schematic diagram of the self-polishing surface antifouling coating of the present invention;

[0024] Figures 2 to 4 This is a test report diagram of antifouling coating on self-polishing surface;

[0025] Figure 5 It is a schematic diagram of the application of antifouling coating on self-polishing surface; DETAILED DESCRIPTION

[0026] The technical scheme in the embodiment of the present invention will be described clearly and completely below. The structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents disclosed in the specification, so that people familiar with this technology can understand and read them, and are not used to limit the limiting conditions that the present invention can implement, so they have no substantial technical significance. Any modification of the structure, change of the proportional relationship, or adjustment of the size should still fall within the scope that the technical content disclosed by the present invention can cover without affecting the effects that the present invention can produce and the purposes that can be achieved. At the same time, the terms such as "upper", "lower", "left", "right", "middle" and so on quoted in this specification are only for the convenience of narration, and are not used to limit the scope that can be implemented. The change or adjustment of the relative relationship should also be regarded as the scope that the present invention can implement without substantially changing the technical content.

[0027] Embodiment 1, a method for preparing a self-polishing surface antifouling coating, comprising the following steps:

[0028] a. The super-hydrophobic and low-surface-energy silica aerogel is crushed into nano-powdered aerogel micropowder particles by ball milling. The particle size of the micropowder particles is less than 80 μm, and the content of the nano-powdered silica aerogel is 0.2% to 15%. ;

[0029] b. The aerogel powder particles obtained in step a are mixed and stirred evenly with the self-polishing antifouling paint to form a coating, wherein the self-polishing antifouling paint comprises the following substances in percentage by mass: 24% xylene, 8% chloroether resin, 5% n-butanol, 15% rosin, 10% zinc oxide, 30% cuprous oxide, and 8% antifouling agent, wherein the antifouling agent is SEA-NINE211; the silica aerogel is mixed evenly with the self-polishing antifouling paint, so that the silica molecules in the silica aerogel are connected with the methyl groups of the self-polishing antifouling paint through a force, thereby forming a microscopic super-hydrophobic low-surface-energy methyl protective film, and the sodium hydroxide molecules of the self-polishing antifouling paint are present in the nano-microporous frame of the silica molecules, thereby forming a microscopic strongly alkaline surface.

[0030] c. The coating obtained in step b is sprayed in multiple layers in batches to form a coating, each coating has a thickness of 150 μm, and sprayed twice to form a paint surface.

[0031] Example 2, the self-polishing antifouling paint comprises the following substances in percentage by mass: 20% xylene, 4% polyamide resin, 4% n-butanol, 15% rosin, 10% zinc oxide, 40% cuprous oxide, and 7% antifouling agent. During the spraying process, the thickness of the first spraying is 50 μm, and the thickness of the second spraying is 150 μm. The rest is the same as Example 1.

[0032] Example 3, the self-polishing antifouling paint comprises the following substances in percentage by mass: 24% xylene, 8% acrylic resin, 1% n-butanol, 13% rosin, 10% zinc oxide, 40% cuprous oxide, and 4% antifouling agent. During the spraying process, the thickness of the first spraying is 150 μm, the thickness of the second spraying is 150 μm, and the thickness of the third spraying is 100 μm. The rest is the same as Example 1.

[0033] Example 4, the self-polishing antifouling paint comprises the following substances in percentage by mass: 15% of xylene, 7% of chloroether resin, 5% of n-butanol, 15% of rosin, 10% of zinc oxide, 40% of cuprous oxide, and 8% of antifouling agent. The rest is the same as Example 1.

[0034] Example 5, the self-polishing antifouling paint comprises the following substances in percentage by mass: 24% of xylene, 8% of polyamide resin, 5% of n-butanol, 8% of rosin, 7% of zinc oxide, 40% of cuprous oxide, and 8% of antifouling agent. The rest is the same as Example 1.

[0035] Example 6, the self-polishing antifouling paint comprises the following substances in percentage by mass: 24% xylene, 8% acrylic resin, 5% n-butanol, 10% rosin, 5% zinc oxide, 40% cuprous oxide, and 8% antifouling agent. The rest is the same as Example 1.

[0036] The super-hydrophobic low-surface-energy silica aerogel in the self-polishing surface antifouling coating has abundant methyl groups -CH3 on the surface of silica molecules and sodium hydroxide NaOH in the nanopores formed by them. Figure 1 The reasons why super-hydrophobic, low-surface-energy silica aerogels are difficult for barnacles, oysters, and seaweed algae to attach and grow on are expressed.

[0037] The self-polishing surface antifouling coating contains super-hydrophobic low-surface-energy aerogel, which makes the surface of the antifouling material have microscopic super-hydrophobic properties, preventing the viscous hydrophilic protein fluid secreted by marine organisms such as barnacles, oysters and shellfish from solidifying and bonding on the microscopic super-hydrophobic low-surface-energy methyl groups. Under the shaking of the water flow, the viscous hydrophilic protein fluid secreted by marine organisms automatically slides down on the surface of the methyl protective film. This is a major principle innovation in the antifouling material to prevent the protein mucus of marine organisms such as barnacles, oysters and shellfish from attaching and solidifying.

[0038] Barnacles have a soft body, secrete viscous hydrophilic and easily solidified body fluids, and strong limbs, which give them strong predation ability, adhesion and solidification on hydrophilic surfaces (rocks, offshore equipment, ships' hydrophilic and easily wetted surfaces), and rapid reproduction ability. The reproduction rate of barnacles is amazing. If they are not properly controlled, they will reproduce in large numbers on the hydrophilic and easily wetted surfaces of rocks, offshore equipment, and ships. When the surface of ships or offshore equipment is protected by aerogel self-polishing surface antifouling materials, the viscous hydrophilic protein fluids secreted by barnacles are prevented from solidifying and bonding on the microscopic super-hydrophobic low-surface-energy methyl groups, and the viscous hydrophilic protein fluids secreted by barnacles automatically slide down under the shaking of the water flow.

[0039] In the super-hydrophobic and low-surface-energy silica aerogel in the self-polishing surface antifouling coating, sodium hydroxide NaOH exists in the nano-micropores composed of silica molecules, which makes the aerogel self-polishing surface antifouling material microscopically strongly alkaline, and its pH value is much greater than the weakly alkaline seawater.

[0040] Seawater is weakly alkaline due to the hydrolysis of weakly acidic anions. The pH of seawater does not change much, generally between 8.0-8.5. The surface seawater is usually stable at around 8-10.2, and the middle and deep seawater generally fluctuates between 7.8-7.5. When the surface of ships or marine equipment is protected by aerogel self-polishing surface antifouling materials, the roots of seaweed algae are prevented from attaching and growing on the microscopic strongly alkaline surface, and the seaweed algae automatically drift away under the shaking of the water flow.

[0041] The nanoporous framework of silica molecules bonded by van der Waals molecular forces in the aerogel of the self-polishing surface antifouling coating is easily broken, which strengthens the self-polishing slow-release performance of the resin in the antifouling material. The silica molecules are bonded by van der Waals molecular forces to form an easily broken nanoporous framework, which is peeled off at 1 / 100 micron level on the surface of the material to self-polish the surface of the material. Because the molecular binding force of silica molecules in the super-hydrophobic low-surface-energy silica aerogel in the aerogel self-polishing surface antifouling material is very small, a small part of the polymer group chain of the chloroether resin is partially blocked by the aerogel micropowder, causing the polymer group of the chloroether resin to be more easily released, making it more difficult for marine organisms to attach and grow.

[0042] The zinc oxide and copper oxide in the self-polishing surface antifouling coating are easier to release and renew on the surface of the material. The zinc oxide and copper oxide mixed in the resin are also easier to slowly release and renew on the surface of the antifouling material due to the fragile aerogel micropowder, making it difficult for marine organisms to attach.

[0043] The aerogel particles in the self-polishing surface antifouling paint make the material more slidable during paint application, the thickness of the sprayed antifouling material layer is more uniform, and it is more closely integrated with the transition paint.

[0044] Under the auspices of the 719 Institute of China Shipbuilding Industry Corporation (internal test), after a year of accelerated test verification of anti-corrosion and anti-fouling hanging pieces (comparison with multiple companies) in Haikou, the preliminary test results show that the steel plate with self-polishing surface anti-fouling coating has anti-corrosion and anti-marine biological adhesion, see comparative test Figure 2-Figure 4 .

[0045] The self-polishing surface antifouling paint is coated to form a self-polishing surface antifouling paint layer 1, which is located on the surface of the connecting and reinforcing paint layer 2, which is located on the surface of the primer antirust paint layer 3, which is located on the surface of the steel plate layer 4.

[0046] Different from the prior art, the self-polishing surface antifouling coating of the present invention and its preparation method and application can have excellent anti-biological attachment performance, good anti-corrosion and anti-fouling performance, and can keep the paint surface smooth.

[0047] The present invention and its embodiments are described schematically above, and the description is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. Therefore, if a person skilled in the art is inspired by it and designs a structural method and an embodiment similar to the technical solution without creativity without departing from the purpose of the invention, they shall all fall within the protection scope of the present invention.

Claims

1. A self-polishing surface antifouling coating, characterized in that: The invention comprises a hydrophobic silica aerogel in the form of nano-powder and a self-polishing antifouling paint, wherein the particle size of the nano-powder of the hydrophobic silica aerogel is less than 80 μm, and each silica molecule of the hydrophobic silica aerogel is connected to three -CH3 methyl groups; the nano-microporous frame of the silica molecules of the silica aerogel contains sodium hydroxide molecules, and the silica molecules in the silica aerogel are combined by van der Waals molecular forces to form an easily breakable nano-microporous frame, and the nano-microporous frame is peeled off at the molecular nano-level on the surface of the material, thereby self-polishing the surface of the material; the silica aerogel powder and the self-polishing antifouling paint are connected to each other, and the silica molecules in the silica aerogel ... The light antifouling paint is mixed evenly, so that the silica aerogel nano-powder is dispersed in the self-polishing antifouling paint. Since the surface of the silica aerogel nano-powder dispersed in the self-polishing antifouling paint is rich in methyl groups, a microscopic super-hydrophobic low-surface-energy methyl protective film is formed on the surface of the paint after curing; the sodium hydroxide molecules of the self-polishing antifouling paint exist in the nano-microporous frame of the silica molecules of the silica aerogel, thereby forming a strongly alkaline surface in the microscopic region; the polymer group chain of the resin in the self-polishing antifouling paint is partially blocked by the silica aerogel powder, so that the polymer group of the resin is easier to release the antifouling agent.

2. The self-polishing surface antifouling coating according to claim 1, characterized in that The pH value of the strongly alkaline surface of the microscopic region is greater than the pH value of the weakly alkaline seawater.

3. The self-polishing surface antifouling coating according to any one of claims 1-2, characterized in that: The self-polishing antifouling paint comprises the following substances in percentage by mass: 15%-24% of xylene, 4%-8% of chloroether resin or polyamide resin or acrylic resin, 1%-5% of n-butanol, 8%-15% of rosin, 5%-10% of zinc oxide, 30%-40% of cuprous oxide, 4%-8% of SEA-NINE211, and the content of nano-powdered hydrophobic silica aerogel is 0.2%-15%.

4. The self-polishing surface antifouling coating according to claim 3, characterized in that The high molecular weight group chain of the chloroether resin, polyamide resin or acrylic resin is partially interrupted by the silicon dioxide aerogel powder, so that the high molecular weight group of the chloroether resin, polyamide resin or acrylic resin is easier to release.

5. A method for preparing a coating formed by a self-polishing surface antifouling paint as claimed in claim 1, characterized in that: The following steps are involved: a. The hydrophobic silica aerogel is crushed into aerogel powder particles by ball milling, and the particle size of the powder particles is less than 80 μm; b. The aerogel powder particles obtained in step a are mixed and stirred with the self-polishing antifouling paint to form a coating; c. The coating prepared in step b is sprayed in multiple layers in batches to form a coating.

6. The method for preparing a coating formed by a self-polishing surface antifouling paint according to claim 5, characterized in that: The coating thickness in step c is 200-400 μm.

7. The method for preparing a coating formed by a self-polishing surface antifouling paint according to claim 6, characterized in that: The coating thickness of each spraying in step c is 50-150 microns.

8. An application of the self-polishing surface antifouling coating as claimed in claim 1, characterized in that: The self-polishing surface antifouling paint is coated to form a self-polishing surface antifouling paint layer, which is located on the surface of the connecting and reinforcing paint layer, which is located on the surface of the primer antirust paint layer, and which is located on the surface of the steel plate layer.

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