In-situ reinforced and modified antistatic sand-erosion resistant coating based on cyclodextrin-modified carbon nanotubes and its preparation method

Abstract

This application relates to the technical field of coatings, specifically to an antistatic, sand-resistant coating that is in-situ reinforced and modified based on cyclodextrin-modified carbon nanotubes, and a method for preparing the same. According to this application, hydroxylated carbon nanotubes are surface-pretreated with a specific diisocyanate, and then cyclodextrin is grafted onto the surface of the pretreated hydroxylated carbon nanotubes to obtain cyclodextrin-modified carbon nanotubes. The cyclodextrin-modified carbon nanotubes are then introduced into a polyurethane resin synthesis process to obtain the polyurethane resin. In this application, the polyurethane resin is further blended with a curing agent as component A to obtain an antistatic, sand-resistant coating.

Description

[Technical Field]

[0001] The present application belongs to the technical field of coatings, and particularly relates to an antistatic, sand-erosion-resistant coating material based on cyclodextrin-modified carbon nanotubes and an in-situ reinforced modified coating material and a method for preparing the same. [Background technology]

[0002] Wind energy is an important renewable energy source, and its large-scale utilization can reduce dependence on fossil fuels, improve the energy structure, protect natural resources, promote regional economic development, and play an important role in responding to increasing global energy demand and climate change.Wind power generation units are a core piece of clean energy and are widely used worldwide. China's cumulative installed wind power capacity in the first half of 2025 has already exceeded 500 million kilowatts, making it an important pillar of China's energy transition.

[0003] Wind turbine blades are one of the core components of wind power generators. During operation, large wind power generators experience relatively high linear velocities of their leading edges, reaching up to 100 m / s or more. Many wind power generators are installed in relatively harsh environments, exposing wind power generator blades to long-term environmental erosion caused by strong ultraviolet rays, wind, sand, rainwater, salt mist, and moist heat. Therefore, blade surface protection is extremely important. Impact of environmental debris on the blade surface during high-speed operation can cause severe erosion damage to the blade, reducing the blade's aerodynamic performance and ultimately damaging the composite structure, directly affecting the power generation efficiency, maintenance costs, and lifespan of the wind power generator. Therefore, protective coatings for wind power generator blades must have excellent sand erosion resistance.

[0004] Furthermore, when blades rotate at high speeds, they rub violently against particulate matter in the air, such as dust, water droplets, and ice crystals, generating and accumulating static charges, creating high surface voltages. The buildup of high static voltages can disrupt the normal operation of sensors on the blades and potentially cause localized corona and spark discharges, damaging the coating and composite blades. Therefore, wind turbine blade paints must have excellent antistatic properties. Therefore, to provide corrosion protection for wind turbine blades, a high-performance sand-erosion-resistant coating with antistatic properties is needed.

[0005] To meet the corrosion protection needs of wind turbine blades, high-performance sand-resistant coating materials must not only have high strength and high elasticity, but also excellent abrasion resistance and adhesion to ensure that the coating is not easily damaged by high-speed gravel abrasion. Furthermore, to meet the long-term protection needs of blades and reduce maintenance costs, high-performance sand-resistant coatings must also have excellent weather resistance. Conventional aromatic polyurethane materials have high strength and a high elastic modulus, but poor weather resistance and lack flexibility, making them unable to meet the requirements for high strength, high elasticity, and weather resistance. Aliphatic elastic polyurethane materials have high elasticity and good weather resistance, but low strength and abrasion resistance, making them unable to withstand high-speed gravel erosion.

[0006] Chinese Patent CN102408824A discloses a polyurethane coating and its preparation method, and the prepared material has good abrasion resistance, adhesion and weather resistance, but does not have antistatic function.

[0007] To achieve antistatic effects, conductive fillers must be added to the coating. Conventional conductive fillers, such as conductive mica and conductive titanium dioxide, require large amounts of filler to achieve antistatic effects. However, excessive filler loading inevitably reduces the coating's strength, abrasion resistance, and other performance characteristics, making it unable to meet the corrosion protection requirements of wind turbine blades. Nanocarbon materials, such as carbon nanotubes, have high bulk conductivity and, assuming effective dispersion, can theoretically achieve antistatic effects at low loadings. However, due to their large specific surface area, they tend to aggregate and are difficult to disperse. Therefore, surface modification is required to achieve good dispersion in resins and achieve antistatic effects.

[0008] In light of this, the development of polyurethane paints that combine high toughness, high abrasion resistance, and excellent antistatic properties, making them suitable for protecting wind turbine blades from sand erosion, is an issue that engineers in this field must address as soon as possible. Summary of the Invention [Problem to be solved by the invention]

[0009] To solve the technical problem that carbon nanotubes are prone to aggregation and are difficult to disperse when used in sand-resistant and anti-static protective paints for wind turbine blades, this application provides an in-situ reinforced and modified anti-static sand-resistant paint based on cyclodextrin-modified carbon nanotubes and a preparation method thereof. [Means for solving the problem]

[0010] According to the present invention, hydroxylated carbon nanotubes are surface-pretreated using a specific diisocyanate, and then cyclodextrin is grafted onto the surface of the pretreated hydroxylated carbon nanotubes to obtain cyclodextrin-modified carbon nanotubes. The cyclodextrin-modified carbon nanotubes are then introduced into a polyurethane resin synthesis process to obtain the polyurethane resin. During the polyurethane synthesis process, polyurethane molecular chain segments are grown in situ on the surface of the cyclodextrin-modified carbon nanotubes, allowing the carbon nanotubes to be stably and uniformly dispersed in the polyurethane resin for a long period of time, resulting in the polyurethane resin exhibiting excellent antistatic properties. Furthermore, the present invention also provides an antistatic, sand-erosion-resistant coating by blending the polyurethane resin as component A with a curing agent.

[0011] A first object of the present application is to provide a hydroxyl-terminated high-molecular-weight polyurethane resin that combines high toughness, high abrasion resistance, and excellent antistatic properties.

[0012] The high molecular weight polyurethane resin is In parts by weight, Polyester polyol A 100 parts by weight, Polyether polyol A: 4 to 18 parts by weight, preferably 7 to 13 parts by weight, for example, 10 parts by weight; Hydroxylated carbon nanotubes: 0.5 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight, for example, 0.8 parts by weight; Cyclodextrin: 5 to 15 parts by weight, preferably 6 to 12 parts by weight, for example, 8 parts by weight; Aliphatic isocyanate A: 25 to 75 parts by weight, preferably 35 to 60 parts by weight, for example, 50 parts by weight; Trimethylolpropane 5 to 20 parts by weight, preferably 8 to 15 parts by weight, for example, 12 parts by weight, Catalyst A: 0.3 to 1.0 parts by weight, preferably 0.5 to 0.75 parts by weight, for example, 0.6 parts by weight; Organic solvent A: 100 to 150 parts by weight, preferably 100 to 130 parts by weight, for example, 120 parts by weight; It is prepared from ingredients containing the following ingredients.

[0013] The polyester polyol A is at least one of polycaprolactone diol and polycarbonate diol.

[0014] The polyester polyol A has a number average molecular weight of 500 to 2,000.

[0015] The polyether polyol A is at least one of polytetramethylene ether glycol and propylene glycol polyether.

[0016] The polyether polyol A has a number average molecular weight of 500 to 2,000.

[0017] The hydroxylated carbon nanotubes are carbon nanotubes that contain hydroxyl functional groups on the surface.

[0018] The cyclodextrin is at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0019] The aliphatic isocyanate A is at least one of isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate).

[0020] The catalyst A is at least one of dibutyltin dilaurate and an organobismuth catalyst.

[0021] The organic solvent A is at least one of dimethylformamide and tetrahydrofuran.

[0022] A second object of the present application is to provide a method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin having high toughness, high abrasion resistance, and excellent antistatic properties as described in the first object of the present application.

[0023] The method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin having high toughness, high abrasion resistance, and excellent antistatic properties comprises the steps of: Step S1: Adding and uniformly dispersing hydroxylated carbon nanotubes to a portion of the organic solvent A, which is 20% to 30% of the total amount of the organic solvent A, to obtain a carbon nanotube dispersion; Step S2 of reacting the carbon nanotube dispersion, a portion of the aliphatic isocyanate A corresponding to 5% to 8% of the total amount of the aliphatic isocyanate A, and a portion of the catalyst A corresponding to 4% to 7% of the total amount of the catalyst A at 60 to 75°C for 1 to 1.5 hours in a nitrogen gas atmosphere to obtain a pretreated carbon nanotube dispersion; Step S3: adding cyclodextrin to the pretreated carbon nanotube dispersion and reacting at 60 to 75°C for 1 to 1.5 hours to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding polyester polyol A, polyether polyol A, the remaining aliphatic isocyanate A, and the remaining organic solvent A to the cyclodextrin-modified carbon nanotube dispersion, and reacting at 60 to 75°C for 1 to 1.5 hours to obtain a first intermediate product; Step S5 of adding a part of the catalyst A, which is 63 to 66% of the total amount of the catalyst A, to the first intermediate product and reacting them at 80 to 90°C for 2 to 3 hours to obtain a second intermediate product; and Step S6 of adding trimethylolpropane and the remaining catalyst A to the second intermediate product and reacting them at 80 to 90°C for 2 to 3 hours to obtain the high molecular weight polyurethane resin.

[0024] In step S2, the active hydroxyl groups (-OH), which are surface-active functional groups of the hydroxylated carbon nanotubes, are chemically reacted with the isocyanate groups (-NCO) of the aliphatic isocyanate A to convert the surfaces of the hydroxylated carbon nanotubes into -NCO groups, which then facilitates chemical grafting of the hydroxylated carbon nanotubes with hydroxyl group-containing cyclodextrin.

[0025] In step S3, the hydroxylated carbon nanotubes whose surfaces have been converted to -NCO groups are reacted with hydroxyl group-containing cyclodextrin, and the cyclodextrin reacts with the NCO groups on the carbon nanotube surface, thereby chemically grafting it onto the surface of the hydroxylated carbon nanotubes, thereby achieving efficient modification of the hydroxylated carbon nanotubes with cyclodextrin.

[0026] In step S4, the cyclodextrin-modified carbon nanotubes still have a large amount of primary hydroxyl groups remaining on the cyclodextrin molecules. The cyclodextrin-modified carbon nanotubes are thoroughly and uniformly mixed with polyester polyol A, polyether polyol A, and aliphatic isocyanate A to undergo a primary polymerization reaction to generate polyurethane molecular chains.

[0027] In step S5, the cyclodextrin-modified carbon nanotubes are further polymerized with the polyester polyol A and the polyether polyol A together with the aliphatic isocyanate A under the action of a catalyst to extend the polyurethane molecular chain.

[0028] In step S6, trimethylolpropane is polymerized under the action of a catalyst to further extend the polyurethane molecular chains, thereby obtaining the high molecular weight polyurethane resin.

[0029] Cyclodextrin molecules have a large-volume, cyclic, rigid three-dimensional structure, and when grafted onto the surface of hydroxylated carbon nanotubes, they exert a steric hindrance effect, effectively preventing the aggregation of hydroxylated carbon nanotubes and significantly improving the dispersibility of hydroxylated carbon nanotubes in the system, thereby achieving effective antistatic effects with a small amount of hydroxylated carbon nanotubes used.

[0030] The cyclodextrin molecules in cyclodextrin-modified carbon nanotubes contain a large amount of primary hydroxyl groups and can participate in the synthesis of polyurethane resin, allowing polyurethane molecular chain segments to grow in situ on the surface of the modified carbon nanotubes, further realizing long-term, stable and uniform dispersion of carbon nanotubes in polyurethane resin. Even with a low loading, the cyclodextrin molecules can form conductive paths, significantly reducing the surface resistivity of the coating film and achieving antistatic effects.

[0031] The cyclodextrin in the cyclodextrin-modified carbon nanotubes has a cyclic rigid three-dimensional structure. When it participates in the polymerization process of polyurethane resin, it functions as a chemical and physical crosslinking point, exerting an in-situ strengthening and modifying effect on the polyurethane resin, significantly improving the mechanical strength and abrasion resistance of the polyurethane resin, and endowing the prepared coating with excellent sand erosion resistance.

[0032] In this application, the synthesis process for incorporating cyclodextrin-modified carbon nanotubes into polyurethane resin is a continuous, uninterrupted process, i.e., cyclodextrin is added to a pre-treated carbon nanotube dispersion to modify the carbon nanotubes, and then polyester polyol A, polyether polyol A, the remaining aliphatic isocyanate A, and the remaining organic solvent A are respectively added to the cyclodextrin-modified carbon nanotube dispersion for in-situ polymerization to form a polyurethane resin. According to this application, polymerization monomers such as polyester polyol A and aliphatic isocyanate A are directly added to the cyclodextrin-modified carbon nanotube dispersion to carry out in-situ polymerization, and polyurethane molecular chains can be directly grown in-situ on the surface of the cyclodextrin-modified carbon nanotubes during the polymerization process, which can more effectively ensure the uniform dispersion of the cyclodextrin-modified carbon nanotubes in the polyurethane resin system.

[0033] The third object of the present invention is to provide an antistatic, sand erosion resistant coating material that is in-situ reinforced and modified based on cyclodextrin-modified carbon nanotubes.

[0034] The antistatic, sand-resistant, and anti-erosion coating material based on the cyclodextrin-modified carbon nanotubes and having in-situ reinforcement and modification comprises component A and component B, the weight ratio of the component A to the component B is 1:0.45 to 0.75, preferably 1:0.5 to 0.6; Component A is a high molecular weight polyurethane resin as described in the first object of the present application, or a high molecular weight polyurethane resin prepared by the preparation method as described in the second object of the present application, The component B is a curing agent.

[0035] The curing agent may be selected from any one or more conventional curing agents that can be used to cure polyurethane resins.

[0036] In view of the structural characteristics of component A, the present inventors have further designed and synthesized a dedicated curing agent, an isocyanate-terminated high molecular weight curing agent, which has a similar structure to the main resin component (component A). Compared with commercially available curing agents, this isocyanate-terminated high molecular weight curing agent has better compatibility with the main resin component, and can further improve the strength, elasticity, and abrasion resistance of the coating.

[0037] In a preferred solution, the curing agent is an isocyanate-terminated high molecular weight curing agent prepared according to the present application; The isocyanate group-terminated high molecular weight curing agent is In parts by weight, Polyester polyol B 100 parts by weight, Polyether polyol B: 8 to 32 parts by weight, preferably 12 to 25 parts by weight, for example, 18 parts by weight; Aliphatic isocyanate B 75 to 125 parts by weight, preferably 80 to 110 parts by weight, for example, 95 parts by weight, Trimethylolpropane 5 to 15 parts by weight, preferably 8 to 15 parts by weight, for example, 12 parts by weight, Catalyst B: 0.3 to 1.0 parts by weight, preferably 0.5 to 0.75 parts by weight, for example, 0.6 parts by weight; Organic solvent B: 100 to 150 parts by weight, preferably 100 to 130 parts by weight, for example, 110 parts by weight; It is prepared from ingredients containing the following ingredients.

[0038] The polyester polyol B is at least one of polycaprolactone diol and polycarbonate diol.

[0039] The number average molecular weight of the polyester polyol B is 500 to 2,000.

[0040] The polyether polyol B is at least one of polytetramethylene ether glycol and propylene glycol polyether.

[0041] The number average molecular weight of the polyether polyol B is 500 to 2,000.

[0042] The aliphatic isocyanate B is at least one of isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate).

[0043] The catalyst B is at least one of dibutyltin dilaurate and an organobismuth-based catalyst.

[0044] The organic solvent B is at least one of dimethylformamide and tetrahydrofuran.

[0045] The polyester polyol A and the polyester polyol B have the same selectable range. In actual practice, the polyester polyol A and the polyester polyol B may be the same or different. For example, the polyester polyol A and the polyester polyol B may both be polycaprolactone diol, or the polyester polyol A may be polycaprolactone diol and the polyester polyol B may be polycarbonate diol.

[0046] The selectable ranges of the polyether polyol A and the polyether polyol B are the same. In actual practice, the polyether polyol A and the polyether polyol B may be the same or different.

[0047] The aliphatic isocyanate A and the aliphatic isocyanate B have the same selectable range. In actual practice, the aliphatic isocyanate A and the aliphatic isocyanate B may be the same or different.

[0048] The selectable range of the catalyst A and the catalyst B is the same. In actual practice, the catalyst A and the catalyst B may be the same or different.

[0049] The selectable range of the organic solvent A is the same as that of the organic solvent B. In actual practice, the organic solvent A and the organic solvent B may be the same or different.

[0050] The method for preparing the isocyanate group-terminated high molecular weight curing agent includes: Step M1: reacting polyester polyol B, polyether polyol B, trimethylolpropane, and organic solvent B in a nitrogen gas atmosphere at 60 to 75°C for 1 to 1.5 hours to obtain a polyol mixture; Step M2 of adding an aliphatic isocyanate B to the polyol mixture and reacting at 60 to 75°C for 1 to 1.5 hours to obtain a third intermediate product; and Step M3 of adding Catalyst B to the third intermediate product and reacting at 80 to 90°C for 2 to 3 hours to obtain the isocyanate-terminated high molecular weight curing agent.

[0051] The antistatic, sand-resistant, and anti-erosion coating material based on cyclodextrin-modified carbon nanotubes and having in-situ reinforcement and modification is provided by the present application. The coating material contains two components, A and B, of which component A is the main component and component B is a curing agent. Before use, components A and B must be uniformly blended together to be cured into a coating film.

[0052] The fourth object of the present application is to provide a method for preparing an antistatic, sand-erosion resistant coating material that is in-situ reinforced and modified based on cyclodextrin-modified carbon nanotubes as described in the third object of the present application.

[0053] The preparation method includes uniformly mixing the component A and the component B according to the amounts used.

[0054] The two-component resin system of component A and component B employed in this application is more suitable for industrial coating processes, and the resin can be cured at room temperature, making it more suitable for use in coatings.

[0055] The antistatic, sand-resistant polyurethane coating film provided by the present application, which is in-situ reinforced and modified based on cyclodextrin-modified carbon nanotubes, simultaneously has high strength, high elasticity, excellent abrasion resistance, high adhesion, weather resistance and excellent antistatic properties, and can meet the demand for sand protection of wind turbine blades.

[0056] The fifth object of the present application is to provide applications in the field of antistatic and sand erosion resistant coating films of the in-situ reinforced and modified antistatic and sand erosion resistant coating film based on the cyclodextrin-modified carbon nanotubes described in the third object of the present application.

[0057] Specifically, the antistatic, sand-resistant, and erosion-resistant coating material, which is in-situ reinforced and modified based on the cyclodextrin-modified carbon nanotubes, is sprayed to a thickness of about 200 micrometers, and then left at room temperature for 14 days or cured at 80°C for 48 hours to obtain a coating film.

[0058] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0059] 1. According to this application, carbon nanotubes are modified by grafting cyclodextrin onto them. Due to their large volume, cyclic, and rigid steric structure, cyclodextrin molecules exert a steric hindrance effect when grafted onto the surface of carbon nanotubes, effectively preventing carbon nanotube aggregation and significantly improving their dispersibility in the system. Cyclodextrin molecules contain a large number of primary hydroxyl groups, allowing them to participate in the polyurethane resin synthesis process, thereby allowing polyurethane molecular chain segments to grow in situ on the surface of the modified carbon nanotubes, further achieving long-term, stable, and uniform dispersion of carbon nanotubes in the polyurethane resin. Conductive pathways can be formed with a low loading, significantly reducing the surface resistivity of the coating film and achieving antistatic effects.

[0060] 2. According to the present invention, cyclodextrin-modified carbon nanotubes are introduced into the synthesis process of polyurethane resin and polymerized in situ. The cyclodextrin molecules with a cyclic rigid conformation are uniformly distributed in the resin system and chemically bonded to the polyurethane resin, functioning as crosslinking points in the polyurethane resin and providing in situ reinforcement to the polyurethane resin, significantly improving the tensile strength and abrasion resistance of the polyurethane resin, thereby producing a polyurethane resin with high strength, high elasticity, and high abrasion resistance.

[0061] 3. The coating film formed by the antistatic, sand-resistant paint in-situ reinforced and modified based on the cyclodextrin-modified carbon nanotubes prepared in this application has a tensile strength of up to 57.5 MPa, a breaking elongation of up to 646%, an abrasion resistance of at least 4.7 mg (1000 g / 1000 r, CS-10), and a surface resistivity of at least 0.9 MΩ / □ (sheet resistivity). At the same time, it has high strength, high elasticity, excellent abrasion resistance, adhesion, weather resistance, and excellent antistatic properties, and can be used for sand protection in fields such as wind turbine blades, propeller blades, high-speed railways, and the undersides of automobile bodies, with broad future applications. [Brief explanation of the drawings]

[0062] [Figure 1] FIG. 1 is a diagram showing the reaction process for preparing high-molecular-weight polyurethane resins according to Examples 1 to 7. DETAILED DESCRIPTION OF THE INVENTION

[0063] The present application will be specifically described below with reference to specific figures and examples. It should be noted that the following examples are for further explanation of the present application and should not be understood as limiting the scope of protection of the present application, and any non-essential improvements and adjustments made to the present application by those skilled in the art based on the contents of the present application will still fall within the scope of protection of the present application.

[0064] All reagents used in the following examples and comparative examples are commercially available. The hydroxylated carbon nanotubes are manufactured by Jiangsu Xianfeng Nanomaterials Technology Co., Ltd. in China, product number XFD02. The polyurethane curing agent N3300 is Desmodur N3390 manufactured by Covestro. The polyurethane curing agent N75 is Desmodur N75 manufactured by Covestro. Isophorone diisocyanate is manufactured by Maclin Corporation in China. 4,4'-methylenebis(cyclohexyl isocyanate) is manufactured by Maclin Corporation in China. The organobismuth catalyst was manufactured by Beijing Boyuan Chemical Co., Ltd., China, product number MC-710. β-cyclodextrin was produced by Shandong Binzhou Zhiyuan Biological Co., Ltd., China. The polycaprolactone diol is the PCL2000 series manufactured by Hunan Juren New Materials Co., Ltd. in China. Polytetramethylene ether glycol is the PTMEG series manufactured by Hangzhou Sanlong New Materials Co., Ltd. in China. The polycarbonate diol is product number YH-206 manufactured by Shandong Yuanli Technology Co., Ltd. in China. The propylene glycol polyether is the DL series manufactured by Shandong Lanxing Dongda Co., Ltd. in China.

[0065] Example 1 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties comprises Component A and Component B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and Component B is an isocyanate-terminated high-molecular-weight curing agent.

[0066] The method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin of component A includes the following steps: Step S1: Add 0.8 parts by weight of hydroxylated carbon nanotubes to 30 parts by weight of dimethylformamide, and ultrasonically disperse the mixture for 30 minutes in an ultrasonic cleaner with an ultrasonic power of 400 W at a stirring speed of 150 r / min to obtain a carbon nanotube dispersion; Step S2: surface pre-treating the carbon nanotubes; i.e., adding the carbon nanotube dispersion, 3 parts by weight of isophorone diisocyanate, and 0.04 parts by weight of an organic bismuth catalyst to a reactor in a nitrogen gas atmosphere, and reacting them at 70°C for 1 hour to obtain a pre-treated carbon nanotube dispersion; Step S3: adding 8 parts by weight of β-cyclodextrin to the pretreated carbon nanotube dispersion and reacting them by heating at 70°C for 1 hour to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 10 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 47 parts by weight of isophorone diisocyanate, and 90 parts by weight of dimethylformamide to the cyclodextrin-modified carbon nanotube dispersion, and reacting them by heating at 75°C for 1 hour to obtain a first intermediate product; Step S5 of adding 0.38 parts by weight of an organic bismuth catalyst to the first intermediate product and reacting them by heating at 90°C for 2 hours to obtain a second intermediate product; and Step S6 of adding 12 parts by weight of trimethylolpropane and 0.18 parts by weight of an organobismuth catalyst to the second intermediate product, and reacting them by heating at 90°C for 3 hours to obtain Component A.

[0067] A schematic diagram of the reaction process for preparing hydroxyl-terminated high molecular weight polyurethane resin is shown in FIG.

[0068] The method for preparing the isocyanate group-terminated high molecular weight curing agent of component B is as follows: Step M1: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 18 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 12 parts by weight of trimethylolpropane, and 110 parts by weight of dimethylformamide to a reaction vessel in a nitrogen gas atmosphere, and reacting them by heating at 70°C for 1 hour to obtain a polyol mixture; Step M2: adding 95 parts by weight of isophorone diisocyanate to the polyol mixture and reacting them by heating at 70°C for 1 hour to obtain a third intermediate product; and step M3 of adding 0.6 parts by weight of an organic bismuth catalyst to the third intermediate product and reacting the mixture by heating at 90°C for 3 hours to obtain component B.

[0069] One part by weight of the component A and 0.55 parts by weight of the component B are uniformly mixed to obtain a polyurethane coating material having high toughness, high abrasion resistance, and excellent antistatic properties.

[0070] Example 2 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties comprises Component A and Component B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and Component B is an isocyanate-terminated high-molecular-weight curing agent.

[0071] The method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin of component A includes the following steps: Step S1: Add 0.8 parts by weight of hydroxylated carbon nanotubes to 30 parts by weight of tetrahydrofuran, and ultrasonically disperse the mixture for 30 minutes in an ultrasonic cleaner with an ultrasonic power of 400 W at a stirring speed of 150 r / min to obtain a carbon nanotube dispersion; Step S2: surface pre-treating the carbon nanotubes; i.e., adding the carbon nanotube dispersion, 3 parts by weight of 4,4'-methylenebis(cyclohexyl isocyanate), and 0.04 parts by weight of dibutyltin dilaurate catalyst to a reactor in a nitrogen gas atmosphere, and reacting them at 70°C for 1 hour to obtain the pre-treated carbon nanotube dispersion; Step S3: adding 8 parts by weight of β-cyclodextrin to the pretreated carbon nanotube dispersion and reacting them by heating at 70°C for 1 hour to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding 100 parts by weight of polycarbonate diol having a number average molecular weight of 2000, 10 parts by weight of propylene glycol polyether having a number average molecular weight of 1000, 47 parts by weight of 4,4'-methylenebis(cyclohexyl isocyanate), and 90 parts by weight of tetrahydrofuran to the cyclodextrin-modified carbon nanotube dispersion, and reacting them by heating at 75°C for 1 hour to obtain a first intermediate product; Step S5 of adding 0.38 parts by weight of dibutyltin dilaurate catalyst to the first intermediate product and reacting them by heating at 90°C for 2 hours to obtain a second intermediate product; and step S6 of adding 12 parts by weight of trimethylolpropane and 0.18 parts by weight of dibutyltin dilaurate catalyst to the second intermediate product, and reacting them by heating at 90°C for 3 hours to obtain component A.

[0072] The method for preparing the isocyanate group-terminated high molecular weight curing agent of component B is as follows: Step M1: in a nitrogen gas atmosphere, adding 100 parts by weight of polycarbonate diol having a number average molecular weight of 2000, 18 parts by weight of propylene glycol polyether having a number average molecular weight of 1000, 12 parts by weight of trimethylolpropane, and 110 parts by weight of tetrahydrofuran to a reaction vessel, and reacting them by heating at 70°C for 1 hour to obtain a polyol mixture; Step M2: adding 95 parts by weight of 4,4'-methylenebis(cyclohexyl isocyanate) to the polyol mixture and reacting by heating at 70°C for 1 hour to obtain a third intermediate product; and step M3 of adding 0.6 parts by weight of dibutyltin dilaurate catalyst to the third intermediate product and reacting by heating at 90°C for 3 hours to obtain component B.

[0073] One part by weight of the component A and 0.55 parts by weight of the component B are uniformly mixed to obtain a polyurethane coating material having high toughness, high abrasion resistance, and excellent antistatic properties.

[0074] Example 3 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties comprises Component A and Component B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and Component B is an isocyanate-terminated high-molecular-weight curing agent.

[0075] The method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin of component A includes the following steps: Step S1: Add 0.5 parts by weight of hydroxylated carbon nanotubes to 20 parts by weight of dimethylformamide, and ultrasonically disperse the mixture for 20 minutes in an ultrasonic cleaner with an ultrasonic power of 400 W while stirring at a stirring speed of 150 r / min to obtain a carbon nanotube dispersion; Step S2: surface pre-treating the carbon nanotubes; i.e., adding the carbon nanotube dispersion, 1.75 parts by weight of isophorone diisocyanate, and 0.02 parts by weight of an organic bismuth catalyst to a reactor in a nitrogen gas atmosphere, and reacting them by heating at 60°C for 1 hour to obtain the pre-treated carbon nanotube dispersion; Step S3: adding 6 parts by weight of β-cyclodextrin to the pretreated carbon nanotube dispersion and reacting them by heating at 60°C for 1 hour to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 1000, 10 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 2000, 33.25 parts by weight of isophorone diisocyanate, and 80 parts by weight of dimethylformamide to the cyclodextrin-modified carbon nanotube dispersion, and reacting them by heating at 60°C for 1 hour to obtain a first intermediate product; Step S5 of adding 0.32 parts by weight of an organic bismuth catalyst to the first intermediate product and reacting them by heating at 80°C for 3 hours to obtain a second intermediate product; and step S6 of adding 8 parts by weight of trimethylolpropane and 0.16 parts by weight of an organobismuth catalyst to the second intermediate product, and reacting them by heating at 80°C for 3 hours to obtain the resin of component A.

[0076] The method for preparing the isocyanate group-terminated high molecular weight curing agent of component B is as follows: Step M1: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 12 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 8 parts by weight of trimethylolpropane, and 100 parts by weight of dimethylformamide to a reaction vessel in a nitrogen gas atmosphere, and reacting them by heating at 60°C for 1 hour to obtain a polyol mixture; Step M2: adding 80 parts by weight of isophorone diisocyanate to the polyol mixture and reacting by heating at 60°C for 1 hour to obtain a third intermediate product; and step M3 of adding 0.5 parts by weight of an organic bismuth catalyst to the third intermediate product and reacting the mixture by heating at 80°C for 3 hours to obtain component B.

[0077] 1 part by weight of the component A and 0.5 parts by weight of the component B are uniformly mixed to obtain a polyurethane coating material having high toughness, high abrasion resistance, and excellent antistatic properties.

[0078] Example 4 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties comprises Component A and Component B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and Component B is an isocyanate-terminated high-molecular-weight curing agent.

[0079] The method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin of component A includes the following steps: Step S1: Add 1.5 parts by weight of hydroxylated carbon nanotubes to 39 parts by weight of dimethylformamide, and ultrasonically disperse the mixture for 30 minutes in an ultrasonic cleaner with an ultrasonic power of 400 W at a stirring speed of 200 r / min to obtain a carbon nanotube dispersion; Step S2: surface pre-treating the carbon nanotubes; i.e., adding the carbon nanotube dispersion, 4.8 parts by weight of isophorone diisocyanate, and 0.05 parts by weight of an organic bismuth catalyst to a reactor in a nitrogen gas atmosphere, and reacting them by heating at 75°C for 1 hour to obtain the pre-treated carbon nanotube dispersion; Step S3: Add 12 parts by weight of β-cyclodextrin to the pretreated carbon nanotube dispersion, and heat and react at 75°C for 1 hour to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 10 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 55.2 parts by weight of isophorone diisocyanate, and 91 parts by weight of dimethylformamide to the cyclodextrin-modified carbon nanotube dispersion, and reacting them by heating at 75°C for 1 hour to obtain a first intermediate product; Step S5 of adding 0.5 parts by weight of an organic bismuth catalyst to the first intermediate product and reacting them by heating at 90°C for 2 hours to obtain a second intermediate product; and Step S6 of adding 15 parts by weight of trimethylolpropane and 0.2 parts by weight of an organobismuth catalyst to the second intermediate product, and reacting them by heating at 90°C for 2 hours to obtain Component A.

[0080] The method for preparing the isocyanate group-terminated high molecular weight curing agent of component B is as follows: Step M1: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 1000, 25 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 2000, 15 parts by weight of trimethylolpropane, and 130 parts by weight of dimethylformamide to a reaction vessel in a nitrogen gas atmosphere, and reacting them by heating at 75°C for 1 hour to obtain a polyol mixture; Step M2: adding 110 parts by weight of isophorone diisocyanate to the polyol mixture and reacting them by heating at 75°C for 1 hour to obtain a third intermediate product; and step M3 of adding 0.75 parts by weight of an organic bismuth catalyst to the third intermediate product and reacting the mixture by heating at 90°C for 2 hours to obtain component B.

[0081] 1 part by weight of the component A and 0.6 parts by weight of the component B are uniformly mixed to obtain a polyurethane coating material having high toughness, high abrasion resistance, and excellent antistatic properties.

[0082] Example 5 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties comprises Component A and Component B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and Component B is an isocyanate-terminated high-molecular-weight curing agent.

[0083] The method for preparing the hydroxyl-terminated high-molecular-weight polyurethane resin of component A includes the following steps: Step S1: Add 0.8 parts by weight of hydroxylated carbon nanotubes to 30 parts by weight of dimethylformamide, and ultrasonically disperse the mixture for 30 minutes in an ultrasonic cleaner with an ultrasonic power of 400 W at a stirring speed of 150 r / min to obtain a carbon nanotube dispersion; Step S2: surface pre-treating the carbon nanotubes; i.e., adding the carbon nanotube dispersion, 3 parts by weight of isophorone diisocyanate, and 0.04 parts by weight of an organic bismuth catalyst to a reactor in a nitrogen gas atmosphere, and reacting them by heating at 70°C for 1 hour to obtain the pre-treated carbon nanotube dispersion; Step S3: adding 8 parts by weight of α-cyclodextrin to the pretreated carbon nanotube dispersion and reacting them by heating at 70°C for 1 hour to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 10 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 47 parts by weight of isophorone diisocyanate, and 90 parts by weight of dimethylformamide to the cyclodextrin-modified carbon nanotube dispersion, and reacting them by heating at 75°C for 1 hour to obtain a first intermediate product; Step S5 of adding 0.38 parts by weight of an organic bismuth catalyst to the first intermediate product and reacting them by heating at 90°C for 2 hours to obtain a second intermediate product; and Step S6 of adding 12 parts by weight of trimethylolpropane and 0.18 parts by weight of an organobismuth catalyst to the second intermediate product, and reacting them by heating at 90°C for 3 hours to obtain Component A.

[0084] The method for preparing the isocyanate group-terminated high molecular weight curing agent of component B is as follows: Step M1: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 18 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 12 parts by weight of trimethylolpropane, and 110 parts by weight of dimethylformamide to a reaction vessel in a nitrogen gas atmosphere, and reacting them by heating at 70°C for 1 hour to obtain a polyol mixture; Step M2: adding 95 parts by weight of isophorone diisocyanate to the polyol mixture and reacting them by heating at 70°C for 1 hour to obtain a third intermediate product; and step M3 of adding 0.6 parts by weight of an organic bismuth catalyst to the third intermediate product and reacting the mixture by heating at 90°C for 3 hours to obtain component B.

[0085] 1 part by weight of the component A and 0.45 parts by weight of the component B are uniformly mixed to obtain a polyurethane coating material having high toughness, high abrasion resistance, and excellent antistatic properties.

[0086] Example 6 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties contains components A and B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and component B is a commercially available polyurethane curing agent, N3300.

[0087] The component A and the method for preparing the paint were the same as in Example 1. The only difference was that component B was replaced with a commonly available polyurethane curing agent, N3300.

[0088] Example 7 The polyurethane coating, which combines high toughness, high abrasion resistance, and excellent antistatic properties, contains components A and B. Component A is a hydroxyl-terminated high-molecular-weight polyurethane resin, and component B is a commercially available polyurethane curing agent N75.

[0089] The component A and the method for preparing the paint were the same as in Example 1. The only difference was that the component B was replaced with the commonly available polyurethane curing agent N75.

[0090] Comparative Example 1 The polyurethane coating contains component A and component B. Component A is a polyurethane resin, and component B is an isocyanate-terminated high-molecular-weight curing agent.

[0091] The only difference between this comparative example and Example 1 is that cyclodextrin is not added during the synthesis of polyurethane resin (component A), step S3 of "adding 8 parts by weight of β-cyclodextrin to the pretreated carbon nanotube dispersion and heating and reacting at 70°C for 1 hour to obtain a cyclodextrin-modified carbon nanotube dispersion" is omitted, and in step S4, "to the cyclodextrin-modified carbon nanotube dispersion" is replaced with "to the pretreated carbon nanotube dispersion," and all other parts are the same as Example 1.

[0092] The method for preparing component B and the paint was the same as in Example 1.

[0093] Comparative Example 2 A polyurethane coating having high toughness, high abrasion resistance, and excellent antistatic properties comprises Component A and Component B. Component A is a polyurethane resin, and Component B is an isocyanate-terminated high-molecular-weight curing agent.

[0094] The method for preparing component B and the paint was the same as in Example 1.

[0095] Compared with Example 1, the only difference in this Comparative Example is that the carbon nanotubes and cyclodextrin are uniformly mixed with the polyurethane resin prepolymer by blending, instead of being introduced into the polyurethane resin synthesis process by in-situ synthesis.

[0096] The method for preparing the polyurethane resin of component A includes the steps of: Step S1: adding 0.8 parts by weight of hydroxylated carbon nanotubes and 8 parts by weight of β-cyclodextrin to 30 parts by weight of dimethylformamide, and ultrasonically dispersing the mixture for 30 minutes in an ultrasonic cleaner with an ultrasonic power of 400 W at a stirring speed of 150 r / min to obtain a dispersion of carbon nanotubes and cyclodextrin; Step S2 of adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 10 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 50 parts by weight of isophorone diisocyanate, and 90 parts by weight of dimethylformamide to a reaction vessel in a nitrogen gas atmosphere, and reacting them by heating at 75°C for 1 hour to obtain a first intermediate product; Step S3 of adding 0.38 parts by weight of an organic bismuth catalyst to the first intermediate product and reacting them by heating at 90°C for 2 hours to obtain a second intermediate product; Step S4: adding 12 parts by weight of trimethylolpropane and 0.22 parts by weight of an organic bismuth catalyst to the second intermediate product, and reacting them by heating at 90°C for 3 hours to obtain the hydroxyl group-terminated high-molecular-weight polyurethane resin prepolymer; and Step S5 of uniformly mixing the dispersion of carbon nanotubes and cyclodextrin with the hydroxyl-terminated high-molecular-weight polyurethane resin prepolymer to obtain Component A.

[0097] The method for preparing the isocyanate group-terminated high molecular weight curing agent of component B is as follows: Step M1: adding 100 parts by weight of polycaprolactone diol having a number average molecular weight of 2000, 18 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000, 12 parts by weight of trimethylolpropane, and 110 parts by weight of dimethylformamide to a reaction vessel in a nitrogen gas atmosphere, and reacting them by heating at 70°C for 1 hour to obtain a polyol mixture; Step M2: adding 95 parts by weight of isophorone diisocyanate to the polyol mixture and reacting them by heating at 70°C for 1 hour to obtain a third intermediate product; and step M3 of adding 0.6 parts by weight of an organic bismuth catalyst to the third intermediate product and reacting the mixture by heating at 90°C for 3 hours to obtain component B.

[0098] The polyurethane coating is obtained by uniformly mixing 1 part by weight of the component A and 0.55 parts by weight of the curing agent of the component B.

[0099] Performance Test The paints prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were sprayed to a thickness of 200 micrometers to form a film, which was then cured at 80°C for 48 hours to obtain a coating film. The coating film was subjected to a performance test.

[0100] The tensile strength was tested according to Chinese standard GB / T 528, the elongation at break was tested according to Chinese standard GB / T 528, the abrasion was tested according to Chinese standard GB / T 1768, the adhesion was tested according to Chinese standard GB / T 5210, and the surface resistivity was tested according to Boeing standard BMS 10-21 (sheet resistance method).

[0101] The test results are shown in Table 1. [Table 1]

[0102] As can be seen from the test results in Table 1, the tensile strength, breaking elongation, and adhesion of the high-performance polyurethane coatings obtained in Examples 1 to 7 were significantly improved, and the abrasion loss and surface resistivity were significantly reduced, compared with Comparative Examples 1 and 2. As can be seen from this, the coating provided by the present application combines high strength, high elasticity, high abrasion resistance, excellent adhesion, and antistatic properties, and can be used to protect wind turbine blades from sand.

[0103] Example 1, Example 6, and Example 7 have the same component A, and the only difference is that component B is different. Example 1 uses a curing agent prepared according to the present application, while Examples 6 and 7 use commercially available polyurethane curing agents N3300 and N75, respectively. Compared with Examples 6 and 7, Example 1 exhibits significantly improved tensile strength, elongation at break, and adhesion, and significantly reduced abrasion and surface resistivity. This demonstrates that, compared with commercially available curing agents, the curing agent prepared according to the present application has better compatibility with the resin main component (component A), further improving the tensile strength, elongation at break, and adhesion of the coating material, and reducing abrasion and surface resistivity, allowing the prepared polyurethane coating material to have higher strength, elasticity, abrasion resistance, and antistatic performance.

[0104] Example 1 and Comparative Example 1 have the same component B (curing agent), and the only difference is that component A is different. Example 1 used a hydroxyl-terminated high molecular weight polyurethane resin prepared according to the present application as component A. Comparative Example 1 did not use cyclodextrin to graft carbon nanotubes for modification, nor did cyclodextrin enter into the polyurethane resin synthesis process. Although the same amount of carbon nanotubes was added, Comparative Example 1 had a significantly higher surface resistivity than Example 1. Compared to Example 1, Comparative Example 1 had significantly lower tensile strength, breaking elongation, and adhesion, and a significantly higher wear volume. As can be seen from these results, grafting and modifying carbon nanotubes with cyclodextrin not only significantly improved the dispersibility of carbon nanotubes in the resin, significantly reduced the surface resistivity of the coating film, and improved the antistatic function, but also allowed the cyclodextrin molecules to participate in the in-situ polymerization process of the polyurethane resin, functioning as chemical crosslinking points in the resin and providing in-situ reinforcement to the resin, significantly improving the tensile strength, abrasion resistance, and adhesion of the coating film.

[0105] Example 1 and Comparative Example 2 have the same component B (curing agent), with the only difference being the component A. Example 1 used a hydroxyl-terminated high molecular weight polyurethane resin prepared according to the present application as component A. The raw materials for component A of the resin in Comparative Example 2 were the same as those in Example 1, except that carbon nanotubes and cyclodextrin were blended into component A rather than being introduced into the polyurethane resin synthesis process by in-situ polymerization. The polyurethane coating prepared in Comparative Example 2 had significantly lower tensile strength, abrasion resistance, and adhesion than Example 1. In particular, the surface resistivity of the coating increased from 2.4 MΩ / □ in Example 1 to 107.2 MΩ / □, significantly deteriorating its antistatic performance. As can be seen from these results, the preparation method adopted in this application, which involves first grafting cyclodextrin onto the surface of carbon nanotubes and then introducing the cyclodextrin-modified carbon nanotubes into the polyurethane resin synthesis process for in situ polymerization, can significantly improve the dispersion stability of carbon nanotubes in the polyurethane resin system, better establish conductive paths, and significantly reduce the surface resistivity of the coating film. In addition, the cyclodextrin-graft-modified carbon nanotubes can participate in the in situ polymerization of polyurethane resin, provide in situ reinforcement for the polyurethane resin, and better improve the tensile strength, abrasion resistance, and adhesion of the coating film.

Claims

1. 1. A method for preparing a hydroxyl-terminated high molecular weight polyurethane resin, comprising: Step S1: Adding and uniformly dispersing hydroxylated carbon nanotubes to a portion of the organic solvent A, which is 20% by weight to 30% by weight of the total amount of the organic solvent A, to obtain a carbon nanotube dispersion; Step S2: reacting the carbon nanotube dispersion, a portion of the aliphatic isocyanate A corresponding to 5% by weight to 8% by weight of the total amount of the aliphatic isocyanate A, and a portion of the catalyst A corresponding to 4% by weight to 7% by weight of the total amount of the catalyst A at 60° C. to 75° C. for 1 to 1.5 hours in a nitrogen gas atmosphere to obtain a pretreated carbon nanotube dispersion; Step S3: adding cyclodextrin to the pretreated carbon nanotube dispersion and reacting at 60 to 75°C for 1 to 1.5 hours to obtain a cyclodextrin-modified carbon nanotube dispersion; Step S4: adding polyester polyol A, polyether polyol A, the remaining aliphatic isocyanate A, and the remaining organic solvent A to the cyclodextrin-modified carbon nanotube dispersion, and reacting at 60 to 75°C for 1 to 1.5 hours to obtain a first intermediate product; Step S5: adding a part of the catalyst A, which is 63% to 66% by weight of the total amount of the catalyst A, to the first intermediate product, and reacting at 80 to 90°C for 2 to 3 hours to obtain a second intermediate product; Step S6: adding trimethylolpropane and the remaining catalyst A to the second intermediate product, and reacting them at 80 to 90°C for 2 to 3 hours to obtain the high molecular weight polyurethane resin; Including, Each component is: In parts by weight, Polyester polyol A 100 parts by weight, Polyether polyol A: 4 to 18 parts by weight, 0.5 to 3 parts by weight of hydroxylated carbon nanotubes, Cyclodextrin 5 to 15 parts by weight, Aliphatic isocyanate A 25 to 75 parts by weight, Trimethylolpropane 5 to 20 parts by weight, Catalyst A 0.3 to 1.0 parts by weight, Organic solvent A is 100 to 150 parts by weight; 1. A method for preparing a hydroxyl-terminated high-molecular-weight polyurethane resin, comprising:

2. The polyester polyol A is at least one of polycaprolactone diol and polycarbonate diol, The polyether polyol A is at least one of polytetramethylene ether glycol and propylene glycol polyether, The hydroxylated carbon nanotubes are carbon nanotubes containing hydroxyl functional groups on the surface thereof, The cyclodextrin is at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, The aliphatic isocyanate A is at least one of isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate), The catalyst A is at least one of dibutyltin dilaurate and an organobismuth catalyst, The organic solvent A is at least one of dimethylformamide and tetrahydrofuran. The method for preparing a hydroxyl-terminated high-molecular-weight polyurethane resin according to claim 1 .

3. The number average molecular weight of the polyester polyol A is 500 to 2000, The number average molecular weight of the polyether polyol A is 500 to 2000. The method for preparing a hydroxyl-terminated high-molecular-weight polyurethane resin according to claim 1 .

4. A method for preparing an in-situ reinforced modified antistatic sand erosion resistant coating based on cyclodextrin-modified carbon nanotubes, comprising: The paint is obtained by mixing component A and component B, the weight ratio of the component A to the component B is 1:0.45 to 0.75; Component A is a high-molecular-weight polyurethane resin obtained by the method for preparing a high-molecular-weight polyurethane resin according to claim 1, Component B is a curing agent. A method for preparing a paint, comprising:

5. the curing agent is an isocyanate group-terminated high molecular weight curing agent, The isocyanate group-terminated high molecular weight curing agent is In parts by weight, Polyester polyol B 100 parts by weight, Polyether polyol B 8 to 32 parts by weight, Aliphatic isocyanate B 75 to 125 parts by weight, Trimethylolpropane 5 to 15 parts by weight Catalyst B 0.3 to 1.0 parts by weight, Organic solvent B 100 to 150 parts by weight, Prepared from ingredients containing the ingredients 5. The method for preparing a paint according to claim 4.

6. The polyester polyol B is at least one of polycaprolactone diol and polycarbonate diol, The number average molecular weight of the polyester polyol B is 500 to 2000, The polyether polyol B is at least one of polytetramethylene ether glycol and propylene glycol polyether, The number average molecular weight of the polyether polyol B is 500 to 2000, The aliphatic isocyanate B is at least one of isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate), the catalyst B is at least one of dibutyltin dilaurate and an organobismuth catalyst; The organic solvent B is at least one of dimethylformamide and tetrahydrofuran.

6. A method for preparing a paint according to claim 5.

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