Anti-icing coating as well as preparation method and application thereof

Abstract

The invention provides an anti-icing coating as well as a preparation method and application thereof. The anti-icing coating comprises a component A and a component B, the component A comprises fluorocarbon resin, modified fluorinated graphene and a first solvent; and the component B comprises modified nano silicon dioxide hollow spheres and isocyanate. The anti-icing coating disclosed by the invention has excellent hydrophobicity, corrosion resistance, weather resistance and photothermal effect through synergistic cooperation of the specific component A and the component B, can effectively inhibit adhesion of water drops and ice crystals and reduce the icing phenomenon, and improves the toughness and impact strength of an anti-icing coating prepared from the coating; and lasting and effective anti-icing and deicing can be realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and relates to an anti-icing coating, a preparation method thereof and uses thereof. Background Art

[0002] As a clean and renewable natural resource with rich reserves and wide distribution, wind energy is an important means to achieve energy transformation and sustainable development goals. Most of the onshore wind farms in China are distributed in the open and cold areas in the northwest, northeast and north China, and the blades are prone to icing in winter. Blade icing will reduce the power output of the unit or cause the unit to shut down, seriously affecting the normal operation of the unit.

[0003] Currently, the most widely used protection method for wind turbine blades is to use a protective coating with a small surface tension. The smaller the surface tension, the larger the contact angle of water on the coating surface, thereby increasing the difficulty of water adhering and icing on the coating surface. Polyurethane, polyurea, acrylic acid, epoxy resin, etc. have good wear resistance and high and low temperature flexibility, and are the resins commonly used in existing wind turbine blade protective coatings, but they do not have anti-icing properties.

[0004] Fluorocarbon resin has many advantages such as low surface energy, heat resistance, weather resistance, chemical resistance, etc., and is a long-lasting and efficient hydrophobic coating. However, the contact angle of a pure perfluorocarbon resin coating does not exceed 120°, the hydrophobic effect is not ideal enough, and the fluorocarbon resin coating has poor toughness and is brittle, and is prone to brittle cracking when impacted. For example, CN118421140A discloses an anti-icing coating, a preparation method thereof and applications thereof. Polysiloxane-modified fluorocarbon resin is used to introduce a silicon-containing group into the main chain or side chain of the fluorocarbon polymer to form a block, graft or interpenetrating network copolymer, so that the coating has better surface lubricity, coating stability and lower surface energy. However, this coating only relies on low surface energy for anti-icing and de-icing, and the water contact angle is greater than 100° and less than 120°, and the hydrophobic effect is not ideal enough. Another example is that CN111607300A discloses a durable anti-icing low surface energy material for wind turbine blades prepared from low surface energy microcapsules, modified hydrophobic silica, polyacrylic acid resin, fluorocarbon resin, leveling agent, dispersant, and solvent, which has the characteristics of superhydrophobicity, anti-icing, self-cleaning, and high weather resistance. However, the preparation process of this system is complex.

[0005] Therefore, how to improve the hydrophobicity, corrosion resistance, weather resistance and anti-icing effect of the anti-icing coating, and improve the strength of the coating is a technical problem to be solved urgently. Summary of the Invention

[0006] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide an anti-icing coating and its preparation method and use. The anti-icing coating of the present invention, through the synergistic cooperation of specific component A and component B, has excellent hydrophobicity, corrosion resistance, weather resistance, and photothermal effect, can effectively inhibit the attachment of water droplets and ice crystals, reduce the icing phenomenon, and improve the toughness and impact resistance of the anti-icing coating obtained from the coating, and can achieve long-lasting and effective anti-icing and de-icing.

[0007] To achieve the purpose of this invention, the following technical solutions are adopted in the present invention:

[0008] In the first aspect, the present invention provides an anti-icing coating, and the anti-icing coating includes component A and component B;

[0009] Component A includes fluorocarbon resin, modified fluorinated graphene, and a first solvent; component B includes modified nano-silica hollow spheres and isocyanate.

[0010] In the present invention, through the synergistic cooperation of component A with specific components and component B with specific components, by constructing a low surface energy and micro-nano structure surface system, not only does the coating have excellent hydrophobicity, corrosion resistance, and weather resistance, effectively inhibit the attachment of water droplets and ice crystals, and reduce the icing phenomenon, but also makes up for the structural defects of the coating during curing and film formation, improves the integrity of the gas film, enhances the coating strength, corrosion resistance, and weather resistance, increases the coating toughness, makes the coating have high impact resistance, ensures that it is not easily damaged under external forces, and extends the service life of the coating. In addition, the photothermal effect of the coating can absorb infrared in sunlight and efficiently convert it into heat energy, generating an obvious temperature rise effect, further preventing icing and promoting the shedding of ice cover, thereby achieving long-lasting and effective anti-icing and de-icing.

[0011] Fluorocarbon resin, as one of the components of component A in the anti-icing coating, has a high bond energy, a small fluorine atom radius, and a large electronegativity, has excellent chemical stability and low surface energy, and shows good hydrophobicity, weather resistance, corrosion resistance, and self-cleaning effect. Modified fluorinated graphene, as one of the components of component A in the anti-icing coating, in addition to having excellent mechanical properties and anti-permeability properties and having a high absorption rate in the far-infrared band, thereby improving the mechanical strength and hardness of the coating obtained from the coating, reducing the microscopic pores and defects of the coating matrix, improving the airtightness and corrosion resistance of the coating, and being able to efficiently convert far-infrared energy into heat energy, preventing icing and promoting the shedding of ice cover, also has good dispersibility and can interact with the interface of fluorocarbon resin, improving the crosslinking density of the coating, and further improving the coating performance.

[0012] The modified nano-silica hollow spheres as one of the components of the coating in component B have the advantages of light texture, strong fluidity, not easy to settle, and easy to coat. In addition, they can also construct a micro-nano structure surface, form a large number of air pockets on the coating surface, greatly increase the gas phase ratio in the solid-liquid contact area, significantly reduce the adhesion between the solid surface and water droplets, and improve the hydrophobicity of the coating. At the same time, the modified nano-silica hollow spheres can also reduce the surface energy, reduce the agglomeration between nanoparticles, improve the dispersion stability and interface compatibility in the coating, and can significantly improve the hydrophobicity and chemical resistance of the coating; further combined with the isocyanate in component B, the phase separation problem of the modified nano-silica hollow spheres in the coating can be solved. At the same time, the isocyanate also plays the role of a curing agent in the coating, which is beneficial to the subsequent coating film formation and improves the film performance.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] Preferably, the anti-icing coating comprises, by mass fraction:

[0015] Component A 50~99 parts

[0016] Component B: 1 to 50 parts.

[0017] For example, the mass fraction of the A component can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 99 parts, etc.; the mass fraction of the B component can be 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts, etc.

[0018] In the present invention, by adjusting the mass fractions between component A and component B within the above range, the hydrophobicity, corrosion resistance, weather resistance, photothermal effect and anti-icing and deicing performance of the anti-icing coating can be better improved.

[0019] Preferably, the A component further comprises an auxiliary agent.

[0020] It should be noted that the present invention does not specifically limit the specific material types of the auxiliary agents. Those skilled in the art can select the auxiliary agents according to actual needs. The auxiliary agents mainly play the roles of wetting, leveling, adhesion or plasticization. For example, the auxiliary agents in the present invention include but are not limited to at least one of BYK-300 leveling agent, BYK-301 leveling agent or ethylene glycol monobutyl ether.

[0021] Preferably, in parts by mass, the component A comprises:

[0022]

[0023]

[0024] For example, the mass fraction of the fluorocarbon resin can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, etc.; the mass fraction of the modified fluorinated graphene can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.; the mass fraction of the first solvent can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc., and the mass fraction of the auxiliary agent can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.

[0025] In the present invention, by controlling the mass fractions of the respective raw materials in component A within the above numerical ranges, the functions of the respective raw materials in the coating can be better exerted, and at the same time, the synergistic cooperation between component A and component B is further enhanced.

[0026] Preferably, by mass fraction, component B includes:

[0027] 1 - 20 parts of modified nano - silica hollow spheres;

[0028] 50 - 90 parts of isocyanate.

[0029] For example, the mass fraction of the modified nano - silica hollow spheres can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.; the mass fraction of the isocyanate can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, etc.

[0030] In the present invention, by controlling the mass fractions of the respective raw materials in component B within the above numerical ranges, not only can the function of component B be better exerted, but also the grafting connection of the active groups on the surface of the modified nano - silica hollow spheres by the isocyanate can be achieved to form a prepolymer of component B, which better improves the phase separation problem of the modified nano - silica hollow spheres in the coating due to the presence of modified groups; at the same time, part of the isocyanate can also act as a curing agent in the coating, which is more beneficial to the film - forming effect of the coating.

[0031] Preferably, the hydroxyl value of the fluorocarbon resin is 50 to 200 mgKOH / g, such as 50 mgKOH / g, 60 mgKOH / g, 70 mgKOH / g, 80 mgKOH / g, 90 mgKOH / g, 100 mgKOH / g, 110 mgKOH / g, 120 mgKOH / g, 130 mgKOH / g, 140 mgKOH / g, 150 mgKOH / g, 160 mgKOH / g, 170 mgKOH / g, 180 mgKOH / g, 190 mgKOH / g or 200 mgKOH / g, etc.

[0032] In the anti-icing coating of the present invention, a fluorocarbon resin with a high hydroxyl value is selected, especially preferably a fluorocarbon resin with a hydroxyl value of 50 to 200 mgKOH / g. During the subsequent curing and film-forming process of the coating, it can react with more curing agents, further increasing the crosslinking density, improving the density of the film, and enhancing the strength, hardness and hydrophobicity of the coating.

[0033] It can be understood that the present invention does not make special limitations on the specific type selection of the fluorocarbon resin, and all types of substances that meet the coating effect are applicable to the present invention.

[0034] For example, the fluorocarbon resin can be selected from any one or a combination of at least two of polyvinylidene fluoride resin, polytetrafluoroethylene resin, hexafluoropropylene resin, ethylene-tetrafluoroethylene copolymer or vinylidene fluoride-hexafluoropropylene copolymer. More preferably, it is any one or a combination of at least two of polytetrafluoroethylene resin, hexafluoropropylene resin or ethylene-tetrafluoroethylene copolymer. The more preferred type of fluorocarbon resin has a higher fluorine content, which can better improve the hydrophobicity and weather resistance of the fluorocarbon resin in the coating.

[0035] Preferably, the modified fluorinated graphene includes silane coupling agent-modified fluorinated graphene.

[0036] In the present invention, after the fluorinated graphene is modified by a silane coupling agent, the silane coupling agent reacts with the surface active groups of the fluorinated graphene to form a covalent bond. The dispersibility in the coating is improved, avoiding its agglomeration in the coating. At the same time, it further enhances the interfacial interaction with the fluorocarbon resin, increases the crosslinking density when the coating is cured to obtain a coating, and improves the coating performance.

[0037] Preferably, the sheet diameter of the unmodified fluorinated graphene is 100 - 2500 nm, such as 100 nm, 250 nm, 500 nm, 750 nm, 1000 nm, 1250 nm, 1500 nm, 1750 nm, 2000 nm, 2250 nm or 2500 nm, etc., and the number of layers is 1 - 20 layers, such as 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers, 10 layers, 11 layers, 12 layers, 13 layers, 14 layers, 15 layers, 16 layers, 17 layers, 18 layers, 19 layers or 20 layers, etc.

[0038] Preferably, the nano - silica hollow spheres include at least two kinds of nano - silica hollow spheres with different median particle sizes, and more preferably include the first median - particle - size nano - silica hollow spheres, the second median - particle - size nano - silica hollow spheres, the third median - particle - size nano - silica hollow spheres and the fourth median - particle - size nano - silica hollow spheres, wherein, the first median particle size > the second median particle size > the third median particle size > the fourth median particle size.

[0039] In the present invention, the unique hollow structure of the nano - silica hollow spheres has high elasticity and high compressive strength, provides support to buffer external impact when stressed, avoids local stress concentration, improves the toughness of the coating, and enhances the impact resistance of the coating. Further, by grading the nano - silica hollow spheres with different median particle sizes, in addition to playing the role after modification, it can also make up for the structural defects generated by the curing of the coating, improve the integrity of the gas film of the coating, and further improve the anti - corrosion and wear - resistance properties of the coating.

[0040] Preferably, the first median particle size is 450 - 550 nm, the second median particle size is 250 - 350 nm, the third median particle size is 75 - 125 nm, and the fourth median particle size is 10 - 60 nm.

[0041] For example, the first median particle size can be 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 510 nm, 520 nm, 530 nm, 540 nm or 550 nm, etc.; the second median particle size can be 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm or 350 nm, etc.; the third median particle size can be 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, 110 nm, 115 nm, 120 nm or 125 nm, etc.; the fourth median particle size can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm or 60 nm, etc.

[0042] In the present invention, the median particle sizes of the regulated nano-silica hollow spheres are preferably within the above numerical ranges, which can better achieve the void filling of the nano-silica hollow spheres. Small-sized particles can penetrate the gaps in the large-particle accumulation body to form a "secondary filling" effect, thereby improving the denseness of the paint film. On the other hand, the small particles also form a uniform stress distribution network in the matrix, enhancing the mechanical properties.

[0043] Preferably, the mass ratio of the first median particle size nano-silica hollow spheres, the second median particle size nano-silica hollow spheres, the third median particle size nano-silica hollow spheres, and the fourth median particle size nano-silica hollow spheres is (1-2):(2-3):(3-4):4, such as 1:2:3:4, 1:3:4:4, 1:3:4:4, 2:2:3:4, or 1.5:2.5:3.5:4, etc.

[0044] Preferably, the modified nano-silica hollow spheres include fluoropolyether-modified nano-silica hollow spheres.

[0045] In the present invention, if the nano-silica hollow spheres are not modified, obvious agglomeration problems will occur in the coating. After fluoropolyether modification, the active terminal hydroxyl groups of the fluoropolyether undergo a condensation reaction with the hydroxyl groups on the surface of the nano-silica hollow spheres to form Si-O-C bonds. By chemical bonding, the fluoropolyether is grafted onto the surface of the nano-silica hollow spheres, which can significantly reduce the surface energy of the nano-silica hollow spheres, reduce the agglomeration between nano-particles, and improve the dispersion stability and interfacial compatibility in the organic coating. The fluoropolyether has excellent hydrophobicity and chemical resistance. Grafting it onto the surface of the nano-silica hollow spheres can significantly improve the surface properties such as hydrophobicity and chemical resistance of the material.

[0046] Preferably, the fluoropolyether-modified nano-silica hollow spheres are subjected to a graft reaction with a partial isocyanate to obtain a prepolymer.

[0047] In the present invention, the high electronegativity and low polarizability of the C-F bonds in the fluoropolyether make the fluoropolyether have extremely low surface tension, showing excellent and stable hydrophobic and oleophobic properties. However, when the fluoropolyether-modified nano-silica hollow spheres are directly added to the coating, especially when added to component A, phase separation problems will occur. The isocyanate groups in the isocyanate can react with the remaining active terminal hydroxyl groups of the fluoropolyether on the surface of the nano-silica hollow spheres to graft the fluoropolyether onto the isocyanate, overcoming the problem that the fluoropolyether cannot be directly blended and modified. Among them, it is preferred to add an excess of isocyanate. One is to react with the remaining active terminal hydroxyl groups of the fluoropolyether, and the other is that when mixed with the fluorocarbon resin, it can also act as a curing agent and react with the hydroxyl groups on the fluorocarbon resin to better cure into a film.

[0048] It should also be noted that the first solvent in the present invention is a selection of conventional technologies, and the types of solvents that can be used in the coatings of the present invention and can be known within a reasonable range by those skilled in the art are all applicable to the present invention.

[0049] For example, the first solvent includes, but is not limited to, any one or a combination of at least two of ethyl acetate, butyl acetate, propylene glycol acetate, propylene glycol methyl ether acetate, toluene, xylene, acetone, dichloromethane, ethylene glycol methyl ether or ethylene glycol ethyl ether.

[0050] In a second aspect, the present invention provides a method for preparing an anti-icing coating as described in the first aspect, and the preparation method includes the following steps:

[0051] Mix fluorocarbon resin, modified fluorinated graphene and the first solvent to obtain component A;

[0052] Mix modified nano-silica hollow spheres and isocyanate to obtain component B;

[0053] Then mix component A and component B to obtain the anti-icing coating.

[0054] In the present invention, after separately preparing component A and component B, and then mixing the two, the synergistic cooperation of each component in different components can be fully exerted, so as to obtain an anti-icing coating with excellent hydrophobicity, corrosion resistance, weather resistance, photothermal effect, which can effectively inhibit the attachment of water droplets and ice crystals, reduce the icing phenomenon, and improve the toughness and impact resistance of the anti-icing coating obtained from the coating, and can achieve long-lasting and effective anti-icing and de-icing; and the preparation method is simple in operation and does not require complex treatment processes.

[0055] Preferably, the mixed raw materials of the A combination further include additives.

[0056] Preferably, the preparation method of the modified fluorinated graphene includes:

[0057] Mix the to-be-modified fluorinated graphene, silane coupling agent and the second solvent for modification to obtain modified fluorinated graphene.

[0058] The present invention does not make special limitations on the more specific preparation method of the modified fluorinated graphene. According to actual needs, the preparation process can be adjusted adaptively to achieve the modification of the fluorinated graphene.

[0059] Optionally, the mass-volume ratio of the graphene fluoride to be modified to the second solvent is (0.3 - 1) g:(40 - 100) mL, such as 0.3 g:40 mL, 0.3 g:60 mL, 0.3 g:100 mL, 0.5 g:40 mL, 0.5 g:60 mL, 0.5 g:100 mL, 0.8 g:40 mL, 0.8 g:60 mL, 0.8 g:100 mL, 1 g:40 mL, 1 g:60 mL or 1 g:100 mL, etc.

[0060] Optionally, the second solvent is selected from anhydrous ethanol.

[0061] Optionally, the mass ratio of the graphene fluoride to be modified to the silane coupling agent is 1:(0.05 - 0.2), such as 1:0.05, 1:0.08, 1:0.09, 1:0.1, 1:0.11, 1:0.12, 1:0.15, 1:0.18 or 1:0.2, etc., and preferably 1:(0.08 - 0.12).

[0062] Optionally, the silane coupling agent includes, but is not limited to, any one or a combination of at least two of 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane or 3-isocyanatophenyltriethoxysilane.

[0063] Optionally, in the preparation process of the modified graphene fluoride, the method of mixing and modification includes stirring, and the stirring speed is 300 - 1000 r / min, such as 300 r / min, 500 r / min, 800 r / min or 1000 r / min, etc.

[0064] Preferably, in the preparation process of the modified graphene fluoride, the temperature of mixing and modification is 60 - 90 °C, such as 60 °C, 70 °C, 80 °C or 90 °C, etc., and the time of mixing and modification is 2 - 6 h, such as 2 h, 3 h, 4 h, 5 h or 6 h, etc.

[0065] In the process of preparing the modified graphene fluoride of the present invention, by regulating the mass-volume ratio of the graphene fluoride to be modified to the second solvent to be (0.3 - 1) g:(40 - 100) mL and / or the mass ratio of the graphene fluoride to be modified to the silane coupling agent to be 1:(0.05 - 0.2) and / or the temperature of mixing and modification to be 60 - 90 °C, the role of the modified graphene fluoride in the coating is better improved.

[0066] Preferably, the preparation method of the modified nano-silica hollow sphere includes:

[0067] Mixing and modifying the nano-silica hollow sphere to be modified, the fluoropolyether modifier and the third solvent to obtain the modified nano-silica hollow sphere.

[0068] It is understandable that the present invention does not limit the detailed process in the preparation method of the modified nano-silica hollow spheres, and can be adaptively selected and adjusted according to actual needs.

[0069] Optionally, the nano-silica hollow spheres to be modified include at least two different median particle size nano-silica hollow spheres, and further preferably include a first median particle size nano-silica hollow sphere, a second median particle size nano-silica hollow sphere, a third median particle size nano-silica hollow sphere and a fourth median particle size nano-silica hollow sphere, wherein the first median particle size > the second median particle size > the third median particle size > the fourth median particle size.

[0070] Optionally, the mass-volume ratio of the total mass of the nano-silica hollow spheres to be modified to the third solvent is 1 g:(20 - 50) mL, such as 1 g:20 mL, 1 g:30 mL, 1 g:40 mL or 1 g:50 mL, etc.

[0071] Optionally, the third solvent includes, but is not limited to, any one or a combination of at least two of methanol, absolute ethanol, isopropanol or butanol.

[0072] Optionally, the mass ratio of the total mass of the nano-silica hollow spheres to be modified to the fluoropolyether is 1:(0.01 - 0.2), such as 1:0.01, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, 1:0.15 or 1:0.2, etc., and preferably 1:(0.05 - 0.1).

[0073] Optionally, the fluoropolyether includes, but is not limited to, any one or a combination of at least two of hydroxyl-terminated perfluoroethylene ether, hydroxyl-terminated perfluoropropylene ether or hydroxyl-terminated perfluoropropylene oxide.

[0074] Optionally, in the preparation process of the modified nano-silica hollow spheres, the method of mixing modification includes stirring, and the stirring speed is 300 - 1000 r / min, such as 300 r / min, 500 r / min, 800 r / min or 1000 r / min, etc.

[0075] Preferably, in the preparation process of the modified nano-silica hollow spheres, the temperature of mixing modification is 60 - 90 °C, such as 60 °C, 70 °C, 80 °C or 90 °C, etc., and the time of mixing modification is 3 - 8 h, such as 3 h, 4 h, 5 h, 6 h, 7 h or 8 h, etc.

[0076] In the process of preparing the modified nano-silica hollow spheres of the present invention, by controlling the mass-volume ratio of the nano-silica hollow spheres to be modified to the third solvent to be 1 g:(20-50) mL and / or the mass ratio of the total mass of the nano-silica hollow spheres to be modified to the fluoropolyether to be 1:(0.01-0.2) and / or the temperature of the mixed modification to be 60-90 °C, the function of the modified nano-silica hollow spheres in the coating is better improved.

[0077] Preferably, the isocyanate includes any one or a combination of at least two of IPDI, HDI, HDI trimer, HMDI or TXDI.

[0078] In a third aspect, the present invention also provides a use of an anti-icing coating, and the use includes using the anti-icing coating as described in the first aspect or the anti-icing coating prepared by the preparation method as described in the second aspect for the anti-icing coating of a wind turbine blade.

[0079] The numerical ranges described in the present invention not only include the exemplified point values above, but also include any point values between the above numerical ranges not exemplified. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the ranges.

[0080] Compared with the prior art, the present invention has the following beneficial effects:

[0081] (1) In the present invention, the A component with specific components and the B component with specific components are synergistically combined to obtain an anti-icing coating with excellent performance; the combination of specific components and components constructs a low surface energy and micro-nano structure surface system, making the coating have excellent hydrophobicity, corrosion resistance, weather resistance, capable of effectively inhibiting the attachment of water droplets and ice crystals, reducing the icing phenomenon; making up for the structural defects of the coating during curing and film formation, improving the integrity of the gas film, increasing the coating strength, corrosion resistance and weather resistance, enhancing the coating toughness, with high coating impact resistance, ensuring that it is not easily damaged under external forces, and extending the service life of the coating; the coating also has a photothermal effect, capable of absorbing infrared in sunlight and efficiently converting it into heat energy, generating an obvious temperature rise effect, further preventing icing and promoting the shedding of ice; thus achieving long-lasting and effective anti-icing and de-icing.

[0082] (2) In the present invention, after separately preparing the A component and the B component and then mixing the two, the synergistic cooperation effect of each component in different components can be fully exerted, obtaining an anti-icing coating with excellent hydrophobicity, corrosion resistance, weather resistance, photothermal effect, capable of effectively inhibiting the attachment of water droplets and ice crystals, reducing the icing phenomenon, and improving the toughness and impact strength of the anti-icing coating obtained from the coating, capable of achieving long-lasting and effective anti-icing and de-icing; and the preparation method is simple to operate and does not require complex treatment processes. Detailed Embodiments

[0083] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0084] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in this application are intended to cover non-exclusive inclusion.

[0085] In the description of this application, technical terms such as "first" and "second" are only used to distinguish different objects and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity, specific order or primary-secondary relationship of the indicated technical features. In the description of the embodiments of this application, "a plurality of" means more than two unless otherwise specifically defined.

[0086] The specific sources of the raw materials used in the following examples and comparative examples are as follows:

[0087] Fluorocarbon resin: Daikin GK-570.

[0088] Graphite fluoride: Cenfluor (Shanghai) Fine Chemical Co., Ltd.

[0089] Nanometer silicon dioxide hollow spheres: Ningbo Teli Technology Co., Ltd.

[0090] 3-Isocyanatopropyltrimethoxysilane: KH-901, Hangzhou Jessica Chemical Co., Ltd.

[0091] 3-Isocyanatopropyltriethoxysilane: KH-907, Hangzhou Jessica Chemical Co., Ltd.

[0092] Hydroxyl-terminated fluoropolyether (hydroxyl-terminated perfluorovinyl ether, hydroxyl-terminated perfluoropropylene ether): Hubei Xinyuhong Biomedical Technology Co., Ltd.

[0093] Isocyanate ( HT-100, HMDI): Wanhua Chemical.

[0094] Isocyanate (IPDI): CAS 4098-71-9.

[0095] Example 1

[0096] This example provides an anti-icing coating, and the anti-icing coating includes 30 g of component A and 5 g of component B;

[0097] Component A comprises 50 g of fluorocarbon resin, 3 g of modified fluorinated graphene, 20 g of the first solvent butyl acetate, and 4 g of an additive (BYK-300);

[0098] Component B comprises 3 g of modified nano-silica hollow spheres and 60 g of isocyanate.

[0099] The preparation method of the anti-icing coating is as follows:

[0100] (1) Preparation of modified fluorinated graphene: Add 5 g of fluorinated graphene into 300 mL of absolute ethanol and perform ultrasonic dispersion for 15 min to obtain a fluorinated graphene dispersion; add 0.5 g of 3-isocyanatopropyltriethoxysilane (KH-901) to the fluorinated graphene dispersion, and carry out heating and stirring at a speed of 500 r / min for 4.5 h, with the heating temperature being 60 °C, to obtain silane coupling agent-modified fluorinated graphene;

[0101] Preparation of modified nano-silica hollow spheres: Place 1 g of nano-silica hollow spheres with a first median particle size of 500 nm, 2 g of nano-silica hollow spheres with a second median particle size of 300 nm, 3 g of nano-silica hollow spheres with a third median particle size of 100 nm, and 4 g of nano-silica hollow spheres with a fourth median particle size of 50 nm in 300 mL of the organic solvent absolute ethanol and perform ultrasonic dispersion for 20 min to obtain a nano-silica hollow sphere dispersion; add 1 g of hydroxyl-terminated perfluoropolyether to the nano-silica hollow sphere dispersion, and carry out heating and stirring at a speed of 500 r / min for 5 h, with the heating temperature being 70 °C, to prepare fluoropolyether-modified nano-silica hollow spheres;

[0102] (2) Preparation of Component A: According to the proportion of 50 g of fluorocarbon resin (Dakin GK-570, hydroxyl value 60 mg KOH / g), 3 g of modified fluorinated graphene, 20 g of butyl acetate, and 4 g of an additive, carry out stirring and mixing at a stirring speed of 300 r / min to obtain Component A;

[0103] Preparation of Component B: According to the proportion of 3 g of modified nano-silica hollow spheres and 60 g of isocyanate ( HT-100, HMDI), carry out stirring and mixing at a stirring speed of 300 r / min to obtain Component B;

[0104] (3) According to the proportion of 30 g of Component A and 5 g of Component B, carry out stirring and mixing at a stirring speed of 300 r / min to obtain the anti-icing coating;

[0105] Note: One part by mass in this example is 1 g.

[0106] Example 2

[0107] This embodiment provides an anti-icing coating, and the anti-icing coating includes 50 g of component A and 1 g of component B;

[0108] Component A includes 30 g of fluorocarbon resin, 5 g of modified fluorinated graphene, 10 g of the first solvent butyl acetate, and 1 g of an auxiliary agent (BYK-301);

[0109] Component B includes 1 g of modified nano-silica hollow spheres and 50 g of isocyanate (CAS 4098-71-9).

[0110] The preparation method of the anti-icing coating is as follows:

[0111] (1) Preparation of modified fluorinated graphene: Add 5 g of fluorinated graphene to 300 mL of absolute ethanol and perform ultrasonic dispersion for 15 min to obtain a fluorinated graphene dispersion; add 0.5 g of 3-isocyanatopropyltriethoxysilane (KH-907) to the fluorinated graphene dispersion, and perform heating and stirring at a rotation speed of 500 r / min for 4.5 h, and the heating temperature is 60 °C to obtain silane-coupling-agent modified fluorinated graphene;

[0112] Preparation of modified nano-silica hollow spheres: Place 1 g of nano-silica hollow spheres with a 500 nm (first median particle size), 2 g of nano-silica hollow spheres with a 300 nm (second median particle size), 3 g of nano-silica hollow spheres with a 100 nm (third median particle size), and 4 g of nano-silica hollow spheres with a 50 nm (fourth median particle size) in 300 mL of the organic solvent absolute ethanol and perform ultrasonic dispersion for 20 min to obtain a nano-silica hollow sphere dispersion; add 1 g of hydroxyl-terminated perfluoropolyether to the nano-silica hollow sphere dispersion, and perform heating and stirring at a rotation speed of 500 r / min for 5 h, and the heating temperature is 70 °C to prepare fluoropolyether-modified nano-silica hollow spheres;

[0113] (2) Preparation of component A: According to the proportion of 30 g of fluorocarbon resin (Daikin GK-570, hydroxyl value is 60 mg KOH / g), 5 g of modified fluorinated graphene, 10 g of butyl acetate, and 1 g of the auxiliary agent, perform stirring and mixing at a stirring speed of 300 r / min to obtain component A;

[0114] Preparation of component B: According to the proportion of 1 g of modified nano-silica hollow spheres and 50 g of isocyanate (CAS 4098-71-9), perform stirring and mixing at a stirring speed of 300 r / min to obtain component B;

[0115] (3) Mix at a stirring speed of 300 r / min according to the ratio of 50 g of component A and 1 g of component B by mass to obtain the anti-icing coating;

[0116] Note: One part by mass in this example is 1 g.

[0117] Example 3

[0118] This example provides an anti-icing coating, and the anti-icing coating includes 99 g of component A and 50 g of component B;

[0119] Component A includes 70 g of fluorocarbon resin, 20 g of modified fluorinated graphene, 50 g of the first solvent butyl acetate, and 20 g of an additive (ethylene glycol monobutyl ether);

[0120] Component B includes 10 g of modified nano-silica hollow spheres and 90 g of isocyanate.

[0121] The preparation method of the anti-icing coating is as follows:

[0122] (1) Preparation of modified fluorinated graphene: Add 5 g of fluorinated graphene to 300 mL of absolute ethanol and perform ultrasonic dispersion for 15 min to obtain a fluorinated graphene dispersion; add 0.5 g of 3-isocyanatopropyltriethoxysilane (KH-901) to the fluorinated graphene dispersion, and perform heating and stirring at a rotation speed of 500 r / min for 4.5 h, with the heating temperature being 60 °C, to obtain silane-coupled modified fluorinated graphene;

[0123] Preparation of modified nano-silica hollow spheres: Place 1 g of nano-silica hollow spheres with a median particle size of 500 nm (the first median particle size), 2 g of nano-silica hollow spheres with a median particle size of 300 nm (the second median particle size), 3 g of nano-silica hollow spheres with a median particle size of 100 nm (the third median particle size), and 4 g of nano-silica hollow spheres with a median particle size of 50 nm (the fourth median particle size) in 300 mL of the organic solvent absolute ethanol and perform ultrasonic dispersion for 20 min to obtain a nano-silica hollow sphere dispersion; add 1 g of hydroxyl-terminated perfluoropolyether to the nano-silica hollow sphere dispersion, and perform heating and stirring at a rotation speed of 500 r / min for 5 h, with the heating temperature being 70 °C, to prepare fluoropolyether-modified nano-silica hollow spheres;

[0124] (2) Preparation of component A: Mix at a stirring speed of 300 r / min according to the ratio of 70 g of fluorocarbon resin (Daikin GK-570, hydroxyl value of 60 mg KOH / g), 20 g of modified fluorinated graphene, 50 g of butyl acetate, and 20 g of an additive by mass of raw materials to obtain component A;

[0125] Preparation of component B: According to the mass of raw materials of 10 g of modified nano-silica hollow spheres and isocyanate ( HT-100, 90 g of HMDI) were stirred and mixed at a stirring speed of 300 r / min to obtain Component B;

[0126] (3) According to the ratio of 99 g of Component A and 50 g of Component B by mass, they were stirred and mixed at a stirring speed of 300 r / min to obtain the anti-icing coating;

[0127] Note: One part by mass in this example is 1 g.

[0128] Example 4

[0129] The difference between this example and Example 1 is that the fluorocarbon resin in this example has a hydroxyl value of 100 mgKOH / g.

[0130] All other conditions were the same as those in Example 1.

[0131] Example 5

[0132] The difference between this example and Example 1 is that the fluorocarbon resin in this example has a hydroxyl value of 200 mgKOH / g.

[0133] All other conditions were the same as those in Example 1.

[0134] Example 6

[0135] The difference between this example and Example 1 is that in the preparation process of the modified silica hollow spheres in this example, 1.5 g of nano-silica hollow spheres with a median particle size of 550 nm (the first median particle size), 2.5 g of nano-silica hollow spheres with a median particle size of 350 nm (the second median particle size), 3.5 g of nano-silica hollow spheres with a median particle size of 125 nm (the third median particle size), and 4 g of nano-silica hollow spheres with a median particle size of 10 nm (the fourth median particle size) were placed in 300 mL of organic solvent anhydrous ethanol and ultrasonically dispersed for 20 min.

[0136] All other conditions were the same as those in Example 1.

[0137] Example 7

[0138] The difference between this example and Example 1 is that in the preparation process of the modified silica hollow spheres in this example, 2 g of nano-silica hollow spheres with a median particle size of 450 nm (the first median particle size), 3 g of nano-silica hollow spheres with a median particle size of 250 nm (the second median particle size), 4 g of nano-silica hollow spheres with a median particle size of 75 nm (the third median particle size), and 4 g of nano-silica hollow spheres with a median particle size of 60 nm (the fourth median particle size) were placed in 300 mL of organic solvent anhydrous ethanol and ultrasonically dispersed for 20 min.

[0139] All other conditions were the same as those in Example 1.

[0140] Example 8

[0141] The difference between this example and Example 1 is that in this example, the fluorocarbon resin has a hydroxyl value of 40 mgKOH / g.

[0142] All other conditions are the same as those in Example 1.

[0143] Example 9

[0144] The difference between this example and Example 1 is that in the preparation process of the modified nano-silica in this example, the nano-silica hollow spheres to be modified include 1 g of nano-silica hollow spheres with a median diameter of 300 nm (the second median diameter), 3 g of nano-silica hollow spheres with a median diameter of 100 nm (the third median diameter), and 4 g of nano-silica hollow spheres with a median diameter of 50 nm (the fourth median diameter); the addition amount of the hydroxyl-terminated perfluoropolyether is adaptively adjusted to 0.9 g.

[0145] All other conditions are the same as those in Example 1.

[0146] Example 10

[0147] The difference between this example and Example 1 is that in the preparation process of the modified nano-silica in this example, the nano-silica hollow spheres to be modified only contain 3 g of nano-silica hollow spheres with a median diameter of 100 nm (the third median diameter); the addition amount of the hydroxyl-terminated perfluoropolyether is adaptively adjusted to 0.3 g.

[0148] All other conditions are the same as those in Example 1.

[0149] Example 11

[0150] The difference between this example and Example 1 is that in this example, the mass fraction of component A is 40 parts.

[0151] All other conditions are the same as those in Example 1.

[0152] Example 12

[0153] The difference between this example and Example 1 is that in component A of this example, the mass fraction of the modified fluorinated graphene is 1 part.

[0154] All other conditions are the same as those in Example 1.

[0155] Example 13

[0156] The difference between this example and Example 1 is that in component B of this example, the mass fraction of the isocyanate is 40 parts.

[0157] All other conditions are the same as those in Example 1.

[0158] Comparative Example 1

[0159] The difference between this comparative example and Example 1 is that in the coating of this comparative example, the A component does not contain modified fluorinated graphene.

[0160] All other conditions are the same as those in Example 1.

[0161] Comparative Example 2

[0162] The difference between this comparative example and Example 1 is that in the coating of this comparative example, the fluorinated graphene in the A component is not subjected to any modification treatment.

[0163] All other conditions are the same as those in Example 1.

[0164] Comparative Example 3

[0165] The difference between this comparative example and Example 1 is that in the coating of this comparative example, the modified fluorinated graphene is in the B component instead of the A component.

[0166] In the preparation method, fluorinated graphene is added to the B component according to the proportion of the corresponding coating as appropriate.

[0167] All other conditions are the same as those in Example 1.

[0168] Comparative Example 4

[0169] The difference between this comparative example and Example 1 is that in the coating of this comparative example, the B component does not contain modified nano-silica hollow spheres.

[0170] All other conditions are the same as those in Example 1.

[0171] Comparative Example 5

[0172] The difference between this comparative example and Example 1 is that in the coating of this comparative example, the nano-silica hollow spheres in the B component are not subjected to any modification treatment.

[0173] All other conditions are the same as those in Example 1.

[0174] Comparative Example 6

[0175] The difference between this comparative example and Example 1 is that in the coating of this comparative example, the modified nano-silica hollow spheres are in the A component instead of the B component.

[0176] In the preparation method, modified nano-silica hollow spheres are added to the A component according to the proportion of the corresponding coating as appropriate.

[0177] All other conditions are the same as those in Example 1.

[0178] Perform performance tests on the anti-icing coatings provided in Examples 1 - 13 and Comparative Examples 1 - 6:

[0179] The anti-icing coatings provided in the examples and comparative examples were respectively sprayed on steel plates of 33 cm × 20 cm (the dry film thickness reached 100 - 120 μm). After they were completely cured, they were placed in a refrigerator at an inclination of about 45°. When the surface temperature of the iron plate was about -15°C, the same amount (1 L) of supercooled water was dropped onto the paint film surface at a given rate, and the icing state of the water droplets was observed. After a certain period of time, the mass of the ice on the steel plate was weighed; the performance of the coating was tested, and the test methods and technical indicators are as described below:

[0180] 1) Contact angle: Measured by a contact angle measuring instrument, technical indicator: > 105°.

[0181] 2) Ice adhesion strength: The ice adhesion strength of the anti-icing coating was measured by the pull-off method using a pull-off strength tester.

[0182] 3) Impact resistance: Tested according to the method of GB / T1732, technical indicator: ≥ 50 cm.

[0183] 4) Surface temperature at 60 s: The initial temperature of the substrate surface was 20°C. Using a solar simulation light source, the surface temperature of the coating was measured after 60 s under a light intensity of 1 kW / m 2 illumination intensity.

[0184] 5) Weather resistance: According to Appendix C of GB / T14522—2008, an artificial weathering test of 600 hours was carried out using a UV340 light source. The paint film did not blister, peel off, or powder.

[0185] 6) Corrosion resistance: According to GB / T1771-1991 "Determination of Resistance to Neutral Salt Spray of Paints and Varnishes", a neutral salt spray (600 h) test was carried out. The paint film did not blister or peel off.

[0186] The test results of the above tests are shown in Table 1.

[0187] Table 1

[0188]

[0189]

[0190]

[0191] In summary, in the present invention, the component A with specific components and the component B with specific components cooperate synergistically to obtain an anti-icing coating with excellent performance; the combination of specific components and components constructs a low surface energy and micro-nano structure surface system, enabling the coating to have excellent hydrophobicity, corrosion resistance, and weather resistance, effectively inhibiting the attachment of water droplets and ice crystals, and reducing the icing phenomenon; it makes up for the structural defects of the coating during curing into a film, improves the integrity of the gas film, enhances the coating strength, corrosion resistance, and weather resistance, increases the coating toughness, and the coating has a high anti-impact ability, ensuring that it is not easily damaged under external forces and extending the service life of the coating; the coating also has a photothermal effect, which can absorb infrared in sunlight and efficiently convert it into heat energy, generating an obvious temperature rise effect to further prevent icing and promote the shedding of ice coating; thus achieving persistent and effective anti-icing and de-icing.

[0192] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An anti-icing coating, characterized in that The anti-icing coating includes component A and component B; Component A includes fluorocarbon resin, modified fluorinated graphene, and a first solvent; component B includes modified nano-silica hollow spheres and isocyanate.

2. The anti-icing coating according to claim 1, characterized in that, By mass fraction, the anti-icing coating includes: Component A: 50 - 99 parts Component B: 1 - 50 parts.

3. The anti-icing coating according to claim 1 or 2, characterized in that, Component A further includes an auxiliary agent; Preferably, by mass parts, component A includes:

4. The anti-icing coating according to claim 1 or 2, characterized in that, By mass parts, component B includes: Modified nano-silica hollow spheres: 1 - 20 parts; Isocyanate: 50 - 90 parts.

5. The anti-icing coating according to claim 1, wherein The hydroxyl value of the fluorocarbon resin is 50 - 200 mgKOH / g.

6. The anti-icing coating according to claim 1, wherein The modified fluorinated graphene includes silane-coupling-agent-modified fluorinated graphene; Preferably, the unmodified fluorinated graphene has a sheet diameter of 100 - 2500 nm and 1 - 20 layers.

7. The anti-icing coating according to claim 1, wherein The nano-silica hollow spheres include at least two different median-particle-size nano-silica hollow spheres, and more preferably include a first median-particle-size nano-silica hollow sphere, a second median-particle-size nano-silica hollow sphere, a third median-particle-size nano-silica hollow sphere, and a fourth median-particle-size nano-silica hollow sphere, where the first median particle size > the second median particle size > the third median particle size > the fourth median particle size; Preferably, the first median particle size is 450 - 550 nm, the second median particle size is 250 - 350 nm, the third median particle size is 75 - 125 nm, and the fourth median particle size is 10 - 60 nm; Preferably, the mass ratio of the first median-particle-size nano-silica hollow sphere, the second median-particle-size nano-silica hollow sphere, the third median-particle-size nano-silica hollow sphere, and the fourth median-particle-size nano-silica hollow sphere is (1 - 2):(2 - 3):(3 - 4):4; Preferably, the modified nano-silica hollow spheres include fluoropolyether-modified nano-silica hollow spheres; Preferably, the fluoropolyether-modified nano-silica hollow spheres and a part of the isocyanate undergo a graft reaction to obtain a prepolymer.

8. A method for preparing an anti-icing coating according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: Mix fluorocarbon resin, modified fluorinated graphene, and the first solvent to obtain component A; Mix modified nano-silica hollow spheres and isocyanate to obtain component B; Then mix component A and component B to obtain the anti-icing coating.

9. The preparation method according to claim 8, characterized in that, The mixed raw materials of component A further include an auxiliary agent; Preferably, the preparation method of the modified fluorinated graphene includes: Mix the fluorinated graphene to be modified, the silane coupling agent, and a second solvent for modification to obtain the modified fluorinated graphene; Preferably, the preparation method of the modified nano-silica hollow spheres includes: Mix the nano-silica hollow spheres to be modified, the fluoropolyether modifier, and a third solvent for modification to obtain the modified nano-silica hollow spheres.

10. Use of an anti-icing coating, characterized in that, The use includes using the anti-icing coating as described in any one of claims 1 - 7 or the anti-icing coating prepared by the preparation method as described in claim 8 or 9 for the anti-icing coating of wind turbine blades.

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