Anti-icing polyurea coating for wind power blade and preparation method of anti-icing polyurea coating

Abstract

The invention belongs to the technical field of coating production, and discloses a wind power blade anti-icing polyurea coating and a preparation method thereof, the coating comprises polyurea and graphene dispersed in the polyurea, the polyurea is fluorine modified polyurea, and the graphene is fluorinated graphene; the mass ratio of the fluorinated graphene to the fluorine-modified polyurea is (2.5-8): 100, the surface energy of the polyurea coating is reduced through fluorine modification, and the hydrophobicity is remarkably improved; the addition of the fluorinated graphene further enhances the far infrared absorption capacity and mechanical properties of the coating, effectively prevents icing and promotes icing to fall off.

Description

Technical Field

[0001] The present application relates to the technical field of coating production, and in particular to an anti-icing polyurea coating for wind turbine blades and a preparation method thereof. Background Art

[0002] Wind energy, a clean, renewable natural resource with abundant reserves and widespread distribution, is a key tool for achieving energy transition and sustainable development goals. my country's onshore wind farms are mostly located in open, cold climates in Northwest, Northeast, and North China, where blades are susceptible to ice formation in winter. Blade ice can reduce turbine power output or cause the unit to shut down, seriously impacting normal operation.

[0003] Currently, hot air heating, electric heating, and hydrophobic anti-icing coatings are the primary methods used to de-ice wind turbine blades. Hot air heating provides uniform heating and reliable operating temperatures, but is difficult to maintain and has low heating efficiency. Electric heating heats the blade surface quickly and is highly efficient, but carries the risk of damage to the heating element over long periods of operation and requires special lightning protection to prevent lightning strikes.

[0004] Hydrophobic anti-icing coatings reduce surface energy and weaken the adhesion between ice and the coating by changing the chemical composition or microstructure of the coating. This method is simple, easy and low-cost, does not require special lightning protection devices, and daily maintenance of the blades is also relatively simple.

[0005] Traditional coatings are difficult to fully reduce surface energy and often use surface micro-nano structures to achieve hydrophobicity and anti-icing. After multiple icing cycles, the surface gradually loses its hydrophobicity, resulting in a decrease in the anti-icing effect or even aggravation of the icing situation; traditional coatings are easily cracked or damaged when impacted and lack impact resistance.

[0006] Chinese patent CN109486269B discloses a super-hydrophobic anti-icing coating, coating and its preparation and application for active photothermal deicing. It is mainly composed of silicon carbide micropowder, carbon nanotubes, adhesive, hydrophobic agent and solvent. The micro-nano structure composed of silicon carbide micropowder and carbon nanotubes has very excellent super-hydrophobic properties. The carbon nanotubes have a strong photothermal effect under near-infrared light irradiation, which realizes the combination of active photothermal deicing and passive anti-icing on the surface of the super-hydrophobic coating for the first time. However, this solution does not give much consideration to the strength and toughness of the coating. During actual operation, there is a risk of damage by wind, sand, raindrops, hail, etc., making it difficult to ensure the stability and durability of the coating during long-term use.

[0007] Chinese patent CN115678396B discloses a polyurea coating material and its use in preparing wind turbine blade coatings. The material comprises component A: a fluoropolyether polyol, an isocyanate, a catalyst, a defoamer, a UV absorber, and a colorant; and component B: a composite polyetheramine and an amine crosslinker. The coating is sprayed onto the surface of the wind turbine blade using a two-component high-pressure spray gun. The material features convenient application, an extremely long service life, self-cleaning properties, and anti-icing capabilities. However, the composite polyetheramine in this scheme requires preparation under high temperature, high pressure, and a catalyst, placing relatively high demands on the preparation process. However, the scheme discloses the use of fluorinated polyether polyols to modify polyureas to enhance their hydrophobicity. Furthermore, Chinese patent CN111662443B discloses a linear polyperfluoroether compound containing hydroxyl groups at its end, and its preparation method, namely, a hydroxyl-terminated perfluoropolyether, which provides a foundation for the preparation of hydroxyl-terminated perfluoropolyether modifiers.

[0008] The problem that this solution needs to solve is: how to provide an anti-icing coating with a relatively simple preparation process and good durable hydrophobic and heat absorption effects. Summary of the Invention

[0009] The purpose of this application is to provide an anti-icing coating with a relatively simple preparation process, a good service life, and good hydrophobic and heat absorption effects, so as to reduce the ice coverage of wind turbine blades by preventing ice coverage and accelerating ice melting.

[0010] The present application combines the advantages of fluorinated polyurea and fluorinated graphene. By modifying polyurea with fluorine, the surface energy of the polyurea coating is reduced, the hydrophobicity of the polyurea coating is improved, and the accumulation of water droplets on the blade surface is reduced; by adding modified fluorinated graphene, the surface energy of the coating is further reduced, and a micro-nano structure is formed on the coating surface, significantly improving the anti-icing performance of the coating; by adding modified fluorinated graphene, the coating's absorption rate and thermal conversion to far-infrared light are enhanced, further preventing icing and promoting the shedding of ice; the polyurea coating of the present application has excellent mechanical properties, weather resistance, and corrosion resistance, and can achieve long-term and effective protection.

[0011] To achieve the above-mentioned object, the present application discloses a wind turbine blade anti-icing polyurea coating, comprising polyurea and graphene dispersed in the polyurea, wherein the polyurea is a fluorine-modified polyurea and the graphene is fluorinated graphene;

[0012] The mass ratio of the fluorinated graphene to the fluorine-modified polyurea is 2.5 to 8:100.

[0013] This application uses fluorinated graphene and the fluorine in fluorinated polyurea to create a unique fluorine-rich interface structure. This structure not only significantly reduces the surface energy of the coating but also, through the strong electronegativity of fluorine atoms, forms a uniform, low-surface-energy, dense interface layer on the coating surface. This design effectively enhances the coating's hydrophobicity while imparting excellent far-infrared absorption.

[0014] Furthermore, the wind turbine blade anti-icing polyurea coating is further added with nano glass beads, the mass ratio of the nano glass beads to the fluorinated graphene is 2 to 5:100, and the particle size of the nano glass beads is 100 to 500 nm.

[0015] The nano-glass beads have a particle size of 100 to 500 nm and possess excellent mechanical strength and thermal stability. Their addition further enhances the coating's wear resistance, impact resistance, and thermal insulation properties, while also creating a synergistic enhancement effect with fluorinated graphene, optimizing the coating's comprehensive protective capabilities. The introduced nano-glass microbeads, through their spherical support structure, create a multi-scale synergistic effect with the fluorinated graphene's lamellar structure. The uniform dispersion of the glass microbeads optimizes the coating's mechanical properties and, combined with the fluorinated graphene's anisotropic thermal conductivity, creates a synergistic thermal management effect, significantly slowing ice crystal nucleation and growth.

[0016] Preferably, the fluorine-modified polyurea is prepared by reacting a fluorine-modified diisocyanate with an amine chain extender to form a polyurea.

[0017] Preferably, the preparation method of the fluorine-modified diisocyanate is specifically as follows: diisocyanate, a terminal hydroxyl perfluoropolyether modifier, and a catalyst are blended and heated in an organic solvent to obtain a fluorine-modified diisocyanate, and the mass ratio of the diisocyanate to the terminal hydroxyl perfluoropolyether modifier is 1:0.01-0.02, and the amount of the catalyst added is 0.1-1% of the total mass of the diisocyanate and the terminal hydroxyl perfluoropolyether modifier.

[0018] Preferably, the diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate;

[0019] The catalyst is selected from at least one of dibutyltin dilaurate, dibutyltin dilaurate, organic zinc, and organic bismuth.

[0020] Preferably, the amine chain extender is selected from isophorone diamine, Clearlink TM 1000、Clearlink TM 3000、Versalink TM 250、Versalink TM 650、Versalink TM1000、Versalink TM 740M, Jefflink TM 555、Jefflink TM 754、Jefflink TM 7027, NH1420, At least one of NH1220, Shenzhen Feiyang F420, and Shenzhen Feiyang F520.

[0021] Preferably, the fluorinated graphene is specifically fluorinated graphene modified by a silane coupling agent, and the silane coupling agent is selected from at least one of KH-550, A-1110, A-1120, KBM-603, KBM-602, A-1130, and Y-5691;

[0022] The modification method is as follows: dispersing the fluorinated graphene in ethanol, then adding a silane coupling agent at a mass ratio of 1:0.03 to 0.15 of the fluorinated graphene to the silane coupling agent, stirring and heating, to obtain the fluorinated graphene modified with the silane coupling agent.

[0023] Preferably, the number of layers of the fluorinated graphene is 1 to 20, and the sheet diameter of the fluorinated graphene is 100 to 2500 nm.

[0024] In addition, the present application discloses a method for preparing the above-mentioned anti-icing polyurea coating for wind turbine blades, which specifically comprises the following steps:

[0025] Step 1: dispersing fluorinated graphene and an amine chain extender in an organic solvent to obtain component A;

[0026] Step 2: Add fluorine-modified diisocyanate to component A at a molar ratio of isocyanate groups in the fluorine-modified diisocyanate to amino groups in the amine chain extender of 1.05 to 1.1:1, stir and mix to obtain an anti-icing polyurea coating for wind turbine blades.

[0027] Preferably, the step 1 is specifically: mixing an amine chain extender, an organic solvent, and an auxiliary agent in a mass ratio of 10-70:10-50:0.5-5, and dispersing the modified fluorinated graphene into the system to obtain component A.

[0028] The organic solvent is selected from at least one of ethyl acetate, butyl acetate, propylene glycol acetate, propylene glycol methyl ether acetate, toluene, xylene, acetone, dichloromethane, ethylene glycol methyl ether, and ethylene glycol ethyl ether;

[0029] The auxiliary agents include a defoaming agent, a leveling agent and an anti-settling agent, and the mass ratio of the defoaming agent, the leveling agent and the anti-settling agent is 0.8-1.2:0.8-1.2:0.8-1.2.

[0030] The beneficial effects of this application are:

[0031] The present application modifies polyurea with fluorine, thereby reducing the surface energy of the polyurea coating, improving the hydrophobicity of the polyurea coating, and reducing the accumulation of water droplets on the blade surface; by adding modified fluorinated graphene, the surface energy of the coating is further reduced, and a micro-nano structure is formed on the coating surface, significantly improving the anti-icing performance of the coating; by adding modified fluorinated graphene, the coating's absorption rate and thermal conversion to far-infrared light are enhanced, further preventing icing and promoting the shedding of ice; the polyurea coating of the present application has excellent mechanical properties, weather resistance, and corrosion resistance, and can achieve long-term and effective protection. DETAILED DESCRIPTION

[0032] The present invention will be described clearly and completely below in conjunction with the examples of the present invention. In the description of the present invention, it should be noted that, where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer were used. Reagents or instruments used where the manufacturer is not specified are conventional products that can be purchased commercially.

[0033] Fluorinated graphene was purchased from Cen Fluor (Shanghai) Fine Chemical Co., Ltd.

[0034] Silane coupling agent was purchased from Hangzhou Jessica Chemical Co., Ltd., model KH-550;

[0035] Hydroxyl-terminated perfluoropolyether was purchased from Quzhou Ruifu Chemical Co., Ltd. with a molecular weight of 4000-6000;

[0036] Dicyclohexylmethane diisocyanate was purchased from Wanhua Chemical, model HMDI;

[0037] Isophorone diisocyanate was purchased from Wanhua Chemical, model IPDI;

[0038] The aliphatic amine chain extender was purchased from Shenzhen Feiyang, model number is Shenzhen Feiyang F420;

[0039] Aliphatic amine chain extenders were purchased from Shandong Jiaying Chemical Technology Co., Ltd. NH1420.

[0040] Silane coupling agent was purchased from Suzhou Huiwangcheng Chemical Co., Ltd., model KBM-603;

[0041] Silane coupling agent was purchased from Guangzhou Shanghe Chemical Technology Co., Ltd., model KBM-602;

[0042] Example 1

[0043] Preparation of modified fluorinated graphene:

[0044] Fluorinated graphene (monolayer, 1500±100 nm in diameter) was added to anhydrous ethanol at a mass ratio of 1:60 and ultrasonically dispersed for 15 min to obtain a fluorinated graphene dispersion.

[0045] KH-550 was added to the fluorinated graphene dispersion at a mass ratio of fluorinated graphene to silane coupling agent of 1:0.08, and the mixture was stirred at 500 r / min and heated to 80° C. for 3 hours to obtain modified fluorinated graphene.

[0046] Preparation of modified aliphatic isocyanates:

[0047] Dicyclohexylmethane diisocyanate ( HMDI) and terminal hydroxyl perfluoropolyether were blended in xylene at a mass ratio of 1:0.015, and 0.3% of dibutyltin dilaurate based on the total mass of dicyclohexylmethane diisocyanate and terminal hydroxyl perfluoropolyether was added, and the mixture was heated at 60°C under a nitrogen atmosphere and reacted for 2 hours to obtain a modified aliphatic isocyanate;

[0048] In the above steps, xylene is used as a solvent, and its mass is 10 times the total mass of dicyclohexylmethane diisocyanate and terminal hydroxyl perfluoropolyether.

[0049] Preparation of anti-icing fluorocarbon resin coating for wind turbine blades:

[0050] Step 1: Mix aliphatic amine chain extender F420, ethyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 50:20:1:1:1, and add modified fluorinated graphene to the above system in a mass ratio of modified fluorinated graphene to polyurea of ​​5:100 and stir to obtain component A;

[0051] Step 2: Component A and component B (modified aliphatic isocyanate) are stirred and mixed according to a molar ratio of the isocyanate group in the fluorine-modified diisocyanate to the amino group in the amine chain extender of 1.08:1 to prepare a polyurea dispersed with fluorinated graphene, i.e., an anti-icing polyurea coating for wind turbine blades.

[0052] Example 2

[0053] Preparation of modified fluorinated graphene:

[0054] Fluorinated graphene (monolayer, 1500±100 nm in diameter) was added to anhydrous ethanol at a mass ratio of 1:60 and ultrasonically dispersed for 15 min to obtain a fluorinated graphene dispersion.

[0055] KBM-602 was added to the fluorinated graphene dispersion at a mass ratio of fluorinated graphene to silane coupling agent of 1:0.03, and the mixture was stirred at 500 r / min and heated to 80° C. for 3 hours to obtain modified fluorinated graphene.

[0056] Preparation of modified aliphatic isocyanates:

[0057] Isophorone diisocyanate ( IPDI) and terminal hydroxyl perfluoropolyether were blended in toluene at a mass ratio of 1:0.01, and 0.1% of dibutyltin dilaurate based on the total mass of dicyclohexylmethane diisocyanate and terminal hydroxyl perfluoropolyether was added, and the mixture was heated at 60°C under a nitrogen atmosphere and reacted for 2 hours to obtain a modified aliphatic isocyanate;

[0058] In the above steps, toluene is used as a solvent, and its mass is 10 times the total mass of isophorone diisocyanate and terminal hydroxyl perfluoropolyether.

[0059] Preparation of anti-icing fluorocarbon resin coating for wind turbine blades:

[0060] Step 1: aliphatic amine chain extender NH1420, butyl acetate, defoamer, leveling agent and anti-settling agent are mixed in a mass ratio of 70:50:0.8:1.2:0.8, and modified fluorinated graphene is added to the above system in a mass ratio of modified fluorinated graphene to polyurea of ​​2.5:100 and stirred to obtain component A;

[0061] Step 2: Component A and component B (modified aliphatic isocyanate) are stirred and mixed according to a molar ratio of the isocyanate group in the fluorine-modified diisocyanate to the amino group in the amine chain extender of 1.05:1 to prepare a polyurea dispersed with fluorinated graphene, i.e., an anti-icing polyurea coating for wind turbine blades.

[0062] Example 3

[0063] Preparation of modified fluorinated graphene:

[0064] Fluorinated graphene (monolayer, 1500±100 nm in diameter) was added to anhydrous ethanol at a mass ratio of 1:60 and ultrasonically dispersed for 15 min to obtain a fluorinated graphene dispersion.

[0065] KBM-603 was added to the fluorinated graphene dispersion at a mass ratio of fluorinated graphene to silane coupling agent of 1:0.15, and the mixture was stirred at 500 r / min and heated to 80° C. for 3 hours to obtain modified fluorinated graphene.

[0066] Preparation of modified aliphatic isocyanates:

[0067] Isophorone diisocyanate ( IPDI) and terminal hydroxyl perfluoropolyether were blended in toluene at a mass ratio of 1:0.02, and 1% of dibutyltin dilaurate based on the total mass of dicyclohexylmethane diisocyanate and terminal hydroxyl perfluoropolyether was added, and the mixture was heated at 60°C under a nitrogen atmosphere and reacted for 2 hours to obtain a modified aliphatic isocyanate;

[0068] In the above steps, toluene is used as a solvent, and its mass is 10 times the total mass of isophorone diisocyanate and terminal hydroxyl perfluoropolyether.

[0069] Preparation of anti-icing fluorocarbon resin coating for wind turbine blades:

[0070] Step 1: Mix aliphatic amine chain extender F420, butyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 20:10:0.8:1.2:0.8, and add modified fluorinated graphene to the above system in a mass ratio of modified fluorinated graphene to polyurea of ​​8:100 and stir to obtain component A;

[0071] Step 2: Component A and component B (modified aliphatic isocyanate) are stirred and mixed according to a molar ratio of the isocyanate group in the fluorine-modified diisocyanate to the amino group in the amine chain extender of 1.1:1 to prepare a polyurea dispersed with fluorinated graphene, i.e., an anti-icing polyurea coating for wind turbine blades.

[0072] Example 4

[0073] The method is basically the same as Example 1, except that multilayer graphene is used instead of single-layer graphene, and the number of graphene layers is about 10 to 20.

[0074] Example 5

[0075] The method is basically the same as Example 1, except that fluorinated graphene with a sheet diameter of 150±50 nm is used instead of fluorinated graphene with a sheet diameter of 1500±100 nm.

[0076] Example 6

[0077] The method is basically the same as Example 1, except that fluorinated graphene with a sheet diameter of 2200±200 nm is used instead of fluorinated graphene with a sheet diameter of 1500±100 nm.

[0078] Example 7

[0079] Basically the same as Example 1, except that a mixture of fluorinated graphene with a sheet diameter of 150±50 nm and fluorinated graphene with a sheet diameter of 2200±200 nm is used to replace the fluorinated graphene with a sheet diameter of 1500±100 nm, and the mass ratio of fluorinated graphene with a sheet diameter of 150±50 nm to fluorinated graphene with a sheet diameter of 2200±200 nm is 3:1.

[0080] Example 8

[0081] The method is basically the same as Example 1, except that step 1 in the method for preparing the anti-icing fluorocarbon resin coating for wind turbine blades is specifically as follows:

[0082] Step 1: Mix the aliphatic amine chain extender F420, ethyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 50:20:1:1:1, and add nanoglass beads and modified fluorinated graphene to the above system in a mass ratio of nanoglass beads, modified fluorinated graphene and polyurea of ​​0.2:5:100 and stir to obtain component A.

[0083] Comparative Example 1

[0084] The method is basically the same as Example 1, except that graphene oxide of the same mass is used instead of graphene fluoride.

[0085] Comparative Example 2

[0086] Preparation of modified aliphatic isocyanates:

[0087] Dicyclohexylmethane diisocyanate ( HMDI) and terminal hydroxyl perfluoropolyether were blended in xylene at a mass ratio of 1:0.015, and 0.3% of dibutyltin dilaurate based on the total mass of dicyclohexylmethane diisocyanate and terminal hydroxyl perfluoropolyether was added, and the mixture was heated at 60°C under a nitrogen atmosphere and reacted for 2 hours to obtain a modified aliphatic isocyanate;

[0088] In the above steps, xylene is used as a solvent, and its mass is 10 times the total mass of dicyclohexylmethane diisocyanate and terminal hydroxyl perfluoropolyether.

[0089] Preparation of coating:

[0090] Step 1: Mix aliphatic amine chain extender F420, ethyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 50:20:1:1:1 to obtain component A;

[0091] Step 2: Component A and component B (modified aliphatic isocyanate) are stirred and mixed according to a molar ratio of the isocyanate group in the fluorine-modified diisocyanate to the amino group in the amine chain extender of 1.08:1 to obtain a polyurea coating.

[0092] Comparative Example 3

[0093] Step 1: Mix aliphatic amine chain extender F420, ethyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 50:20:1:1:1 to obtain component A;

[0094] Step 2: Component A and component B (dicyclohexylmethane diisocyanate) were stirred and mixed according to a molar ratio of isocyanate groups in the diisocyanate to amino groups in the amine chain extender of 1.08:1 to obtain a polyurea coating.

[0095] Comparative Example 4

[0096] Preparation of modified fluorinated graphene:

[0097] Fluorinated graphene (monolayer, 1500±100 nm in diameter) was added to anhydrous ethanol at a mass ratio of 1:60 and ultrasonically dispersed for 15 min to obtain a fluorinated graphene dispersion.

[0098] KH-550 was added to the fluorinated graphene dispersion at a mass ratio of fluorinated graphene to silane coupling agent of 1:0.08, and the mixture was stirred at 500 r / min and heated to 80° C. for 3 hours to obtain modified fluorinated graphene.

[0099] Preparation of coating:

[0100] Step 1: Mix aliphatic amine chain extender F420, ethyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 50:20:1:1:1, and add modified fluorinated graphene to the above system in a mass ratio of modified fluorinated graphene to polyurea of ​​5:100 and stir to obtain component A;

[0101] Step 2: Component A and component B (dicyclohexylmethane diisocyanate) were stirred and mixed according to a molar ratio of isocyanate groups in the diisocyanate to amino groups in the amine chain extender of 1.08:1 to obtain a polyurea coating.

[0102] Comparative Example 5

[0103] Preparation of modified graphene oxide:

[0104] Graphene oxide (monolayer, 1500±100 nm in diameter) was added to anhydrous ethanol at a mass ratio of 1:60 and ultrasonically dispersed for 15 min to obtain a graphene oxide dispersion.

[0105] KH-550 was added to the graphene oxide dispersion at a mass ratio of graphene oxide to silane coupling agent of 1:0.08, and the mixture was stirred at 500 r / min and heated to 80° C. for 3 hours to obtain modified graphene oxide.

[0106] Preparation of coating:

[0107] Step 1: Mix aliphatic amine chain extender F420, ethyl acetate, defoamer, leveling agent and anti-settling agent in a mass ratio of 50:20:1:1:1, and add modified graphene oxide to the above system in a mass ratio of modified graphene oxide to polyurea of ​​5:100 and stir to obtain component A;

[0108] Step 2: Component A and component B (dicyclohexylmethane diisocyanate) are stirred and mixed according to a molar ratio of isocyanate groups in the isocyanate to amino groups in the amine chain extender of 1.08:1 to obtain a polyurea coating.

[0109] Performance Testing

[0110] Contact angle: Contact angle measurement is carried out according to GB / T 23764.

[0111] Ice adhesion strength: According to GB / T 5210 "Determination of adhesion of coatings - Pull-off method", the ice adhesion strength of the anti-icing coating is measured by the pull-off method using a pull-off strength tester.

[0112] Surface temperature at 60S: Initial surface temperature of substrate is 20℃, using solar simulated light source at 1kW / m 2 Measure the coating surface temperature after 60 seconds of exposure to intense light. Measure the coating surface temperature at a specific time (e.g., 60 seconds) to evaluate its temperature rise performance. The higher the temperature rise, the better the photothermal effect and the better the anti-icing effect.

[0113] Table 1

[0114]

[0115] Result analysis:

[0116] 1. Examples 1-3 show that when the raw materials and process parameters in the production process of the wind turbine blade anti-icing polyurea coating are slightly adjusted, the hydrophobicity, heat absorption capacity, and ice adhesion strength of Examples 1-3 show a certain degree of fluctuation, but the overall fluctuation range is relatively small.

[0117] 2. As shown in Example 4, when multilayer graphene is used instead of single-layer graphene, the ice adhesion strength of Example 4 is significantly increased compared to Example 1, while the heat absorption effect is significantly reduced. This phenomenon may be due to the fact that the single-layer structure has less scattering, resulting in highly concentrated and rapid heat generation. Its large specific surface area facilitates the rapid transfer of generated heat to the surrounding medium. However, multilayer graphene has more layers and more scattering, and its heat transfer capacity may be reduced compared to a single layer.

[0118] Further observation of Examples 5-7 shows that, firstly, the heat absorption effect of using large-diameter fluorinated graphene or small-diameter fluorinated graphene alone has a trend of improvement compared to Example 1 to varying degrees. The reason may be that large-diameter graphene can form a larger area of ​​continuous coverage in the coating. This greatly reduces the area not covered by graphene in the coating, making it more difficult for incident light to directly penetrate the coating; and graphene with an ultra-small diameter (150±50nm) has an extremely high specific surface area. This means that at the same addition amount, more graphene is exposed to the incident light, providing a richer absorption site for incident light, thereby enhancing the heat absorption effect.

[0119] Further observation of Example 7 shows that when Example 7 uses a mixture of fluorinated graphene with a flake diameter of 150±50 nm and fluorinated graphene with a flake diameter of 2200±200 nm, its heat absorption effect is further enhanced. The reason may be that the light is continuously scattered by the graphene with a small flake diameter and the heat is transferred by the graphene with a large flake diameter, which improves the utilization rate of the incident light and ultimately improves the heat absorption capacity of the coating.

[0120] 4. As can be seen from Example 1 and Comparative Example 1, when graphene oxide is used instead of graphene fluoride in Comparative Example 1, the heat absorption effect of Comparative Example 1 is significantly reduced compared with Example 1;

[0121] Further observation of Comparative Examples 2-5 shows that when the polyurea used is a non-fluorine-modified polyurea (i.e., a polyurea prepared using a non-fluorine-modified diisocyanate), the heat absorption effect of Comparative Examples 4-5 is indeed improved relative to that of Comparative Example 3 and even Comparative Example 2, which indicates that the addition of graphene can improve the heat absorption capacity of the coating. However, the difference in heat absorption effect between Comparative Examples 4-5 is not large. It can be seen that in the use of non-fluorine-modified polyurea, the heat absorption enhancement ability of fluorinated graphene and graphene oxide is similar;

[0122] Looking back at the difference in heat absorption effect between Example 1 and Comparative Example 1, the two showed a significant performance gap when further using fluorine-modified polyurea. The reason may be that the fluorinated graphene has a higher similarity with the fluorine-modified polyurea and is more evenly dispersed in the fluorine-modified polyurea, thereby improving the overall heat absorption capacity of the material.

[0123] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A wind turbine blade anti-icing polyurea coating, characterized in that: The invention comprises polyurea and graphene dispersed in the polyurea, wherein the polyurea is fluorine-modified polyurea and the graphene is fluorinated graphene; The mass ratio of the fluorinated graphene to the fluorine-modified polyurea is 2.5 to 8:

100.

2. The anti-icing polyurea coating for wind turbine blades according to claim 1, characterized in that: Nano glass beads are further added to the wind turbine blade anti-icing polyurea coating, the mass ratio of the nano glass beads to the fluorinated graphene is 2-5:100, and the particle size of the nano glass beads is 100-500 nm.

3. The anti-icing polyurea coating for wind turbine blades according to claim 1, characterized in that: The fluorine-modified polyurea is prepared by polyurea reaction between fluorine-modified diisocyanate and an amine chain extender.

4. The anti-icing polyurea coating for wind turbine blades according to claim 3, characterized in that: The preparation method of the fluorine-modified diisocyanate is specifically as follows: diisocyanate, a terminal hydroxyl perfluoropolyether modifier, and a catalyst are blended in an organic solvent and heated to obtain the fluorine-modified diisocyanate, wherein the mass ratio of the diisocyanate to the terminal hydroxyl perfluoropolyether modifier is 1:0.01-0.02, and the amount of the catalyst added is 0.1-1% of the total mass of the diisocyanate and the terminal hydroxyl perfluoropolyether modifier.

5. The anti-icing polyurea coating for wind turbine blades according to claim 4, characterized in that: The diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate; The catalyst is selected from at least one of dibutyltin dilaurate, dibutyltin dilaurate, organic zinc, and organic bismuth.

6. The anti-icing polyurea coating for wind turbine blades according to claim 3, characterized in that: The amine chain extender is selected from isophorone diamine, Clearlink TM 1000、Clearlink TM 3000、Versalink TM 250、Versalink TM 650、Versalink TM 1000、Versalink TM 740M, Jefflink TM 555、Jefflink TM 754、Jefflink TM 7027, NH1420, At least one of NH1220, Shenzhen Feiyang F420, and Shenzhen Feiyang F520.

7. The anti-icing polyurea coating for wind turbine blades according to claim 1, characterized in that: The fluorinated graphene is specifically fluorinated graphene modified by a silane coupling agent, and the silane coupling agent is selected from at least one of KH-550, A-1110, A-1120, KBM-603, KBM-602, A-1130, and Y-5691; The modification method is as follows: dispersing the fluorinated graphene in ethanol, then adding a silane coupling agent at a mass ratio of fluorinated graphene to silane coupling agent of 1:0.03-0.15, stirring and heating to obtain the fluorinated graphene modified with the silane coupling agent.

8. The anti-icing polyurea coating for wind turbine blades according to claim 1, characterized in that: The number of layers of the fluorinated graphene is 1 to 20, and the sheet diameter of the fluorinated graphene is 100 to 2500 nm.

9. A method for preparing the anti-icing polyurea coating for wind turbine blades according to any one of claims 3 to 8, characterized in that: The specific steps include: Step 1: dispersing fluorinated graphene and an amine chain extender in an organic solvent to obtain component A; Step 2: Add fluorine-modified diisocyanate to component A at a molar ratio of isocyanate groups in the fluorine-modified diisocyanate to amino groups in the amine chain extender of 1.05 to 1.1:1, stir and mix to obtain an anti-icing polyurea coating for wind turbine blades.

10. The method for preparing the anti-icing polyurea coating for wind turbine blades according to claim 9, characterized in that: The step 1 specifically comprises: mixing an amine chain extender, an organic solvent, and an auxiliary agent in a mass ratio of 10-70:10-50:0.5-5, and dispersing the modified fluorinated graphene into the system to obtain component A; The organic solvent is selected from at least one of ethyl acetate, butyl acetate, propylene glycol acetate, propylene glycol methyl ether acetate, toluene, xylene, acetone, dichloromethane, ethylene glycol methyl ether, and ethylene glycol ethyl ether; The auxiliary agents include a defoaming agent, a leveling agent and an anti-settling agent, and the mass ratio of the defoaming agent, the leveling agent and the anti-settling agent is 0.8-1.2:0.8-1.2:0.8-1.2.

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