A photothermal conversion super-hydrophobic wind turbine blade surface protective coating and preparation method thereof

Abstract

The present invention discloses a photothermal conversion super-hydrophobic wind turbine blade surface protective coating and a preparation method thereof. The coating is mainly composed of a fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by a photothermal conversion modified nano slurry. On the one hand, the dispersion effect of the photothermal conversion nano slurry is improved. On the other hand, the evenly dispersed photothermal conversion nano particles ensure the photothermal conversion effect of the super-hydrophobic wind turbine blade surface protective coating coating, making the surface moisture of the coating easy to volatilize and difficult to freeze. Even if it freezes, it has the advantage of being easy to melt and drip. Compared with the wind turbine blade surface protective coating with a single function and an insufficient anti-icing effect on the current market, the photothermal conversion super-hydrophobic wind turbine blade surface protective coating of the present invention has a particularly outstanding anti-icing effect, and the ice adhesion is as low as below 20kPa; at the same time, the coating also has the advantages of simple and easy process, environmental protection, resistance to wet and heat aging and ultraviolet aging, acid resistance, and safe use.

Description

Technical Field

[0001] The present invention relates to a wind turbine blade surface protective coating and a preparation method thereof, and in particular to a photothermal conversion super-hydrophobic wind turbine blade surface protective coating and a preparation method thereof; and belongs to the technical field of coatings. Background Art

[0002] Social and economic development requires huge energy consumption, and traditional fossil energy faces serious problems such as insufficient resources and serious pollution. Wind energy is a clean and renewable energy source. Wind power generation is not only a supplement to my country's conventional electricity, but also a trend in the future development of electricity. It is increasingly used in large-scale wind farms and some places with isolated power supply. Due to the increase in air density at lower temperatures, the available wind power is higher than other places. Therefore, wind farms built on cold mountains can produce more efficient power generation efficiency. At the same time, the Chinese government strongly encourages the development of wind power generation. With the maturity of wind power generation technology, wind energy will become the most important sustainable energy source.

[0003] Wind turbine blades are an important part of wind power generation equipment. With the large-scale development of the wind power generation industry, the icing problem faced by wind turbine blades has become more and more prominent, especially in areas with humid climates in winter and spring. The icing of wind turbine blades has become the main factor affecting the normal operation of wind farms. After the blades are covered with ice, the aerodynamic characteristics of the blades change and the dynamic load of the unit increases, which will have a negative impact on the safe operation and benefits of the wind farm. The output power of the wind turbine will change greatly. Relatively light icing will cause a part of the blade power loss, while severe icing will cause its output power to be zero, and it will stop running. This drawback has become an important factor restricting the development and construction of wind farms in cold areas. Therefore, anti-icing and de-icing problems have also become a difficult problem to be solved in the field of wind power. The anti-icing and de-icing technology of wind turbine blades in cold areas is of great significance to the safe, economical and efficient operation of wind farms and large wind turbines. The current development of science and technology has limitations and cannot fundamentally eliminate the icing problem. Usually, necessary measures can only be taken immediately after the icing occurs to remove the icing, which can effectively reduce economic losses. Therefore, preventing wind turbine blades from icing in advance becomes an effective technical means, and coating with super-hydrophobic coating is the simplest method to prevent and de-ice wind turbine blades.

[0004] The invention patent with application number 202011256664.6 discloses an energy-absorbing super-amphiphobic anti-icing coating for wind turbine blades and its preparation method. The coating is composed of the following raw materials in parts by weight: 8 to 15 parts of super-amphiphobic modified nano-carbon tubes, 2 to 5 parts of porous filler powder, 45 to 70 parts of modified resin, 2 to 4 parts of dispersant, 1 to 2 parts of defoaming agent, 2 to 3 parts of leveling agent, and 15 to 27 parts of solvent. The wind turbine blades using the coating have the function of preventing icing. The invention patent with application number 201711038796.X discloses an anti-icing wind turbine blade and a preparation method thereof. The outer surface of the wind turbine blade is coated with a layer of coating, which includes the following ingredients in weight ratio: 20-30 parts of resin, 1-2 parts of dispersant, 10-14 parts of pigment, 0.01-3 parts of conductive material, 0.2-0.4 parts of defoamer, 0.1-0.2 parts of leveling agent, 1-3 parts of rheological additive, 3-5 parts of matting agent, 2-4 parts of adhesion promoter, 0.01-0.5 parts of initiator, 3-10 parts of butyl acetate, 5-8 parts of propylene glycol methyl ether acetate, 6-10 parts of light calcium carbonate, 0.5-0.9 parts of anti-precipitation fumed silica, and 0.2-0.3 parts of xylene. After spraying with the coating, the weather resistance, hydrophobicity, impact resistance and wear resistance of the blade are improved.

[0005] However, the existing coating anti-icing technology cannot fundamentally solve the blade icing problem. It can only delay icing to a certain extent to shorten the blade icing cycle. In addition, it has a single function, the life of the coating itself is generally short, and the anti-icing effect is not prominent enough. With the development of society and the advancement of science and technology, wind turbine blade anti-icing coatings not only need to have good anti-icing and deicing effects, but also need to be environmentally friendly, safe to use and have long-lasting deicing properties. Therefore, the development of coatings with good anti-icing and deicing effects, integrating environmental protection, scratch resistance, weather resistance, hydrophobic stability and other characteristics, while being able to reduce ice on the coating surface and improve the photothermal conversion effect of nano-slurry has become the development trend of wind turbine blade anti-icing coatings and has broad application prospects. Summary of the invention

[0006] One of the purposes of the present invention is to provide a photothermal conversion super-hydrophobic wind turbine blade surface protective coating to address the above-mentioned problems existing in the prior art; the second purpose is to provide a method for preparing the photothermal conversion super-hydrophobic wind turbine blade surface protective coating.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] The present invention first discloses a photothermal conversion super-hydrophobic wind turbine blade surface protective coating, which is compounded by the following components in parts by weight:

[0009] 100 parts of fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by photothermal conversion nano slurry;

[0010] 15-35 parts of micro-nano particle / fluorinated silane coupling agent modified slurry;

[0011] 2 to 5 parts of curing agent;

[0012] 1-2 parts of leveling agent;

[0013] 0.5 to 1 part of defoaming agent.

[0014] Preferably, the aforementioned curing agent is a commercial waterborne polyurethane curing agent; the leveling agent is polyorganosiloxane, polyether-modified polyorganosiloxane or fluorine-containing surfactant; and the defoaming agent is a waterborne silicone defoaming agent.

[0015] The present invention also discloses a method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating as described above, comprising the following steps:

[0016] S1. Preparation of photothermal conversion modified nano-slurry

[0017] A mixed solution of 5 parts by mass of photothermal conversion two-dimensional nanoparticles, 20 parts by mass of tetrachloroethylene, 1 to 2 parts by mass of an intercalant and 0.5 to 1.5 parts by mass of an aliphatic or alicyclic diisocyanate is added to a reaction container, heated to 60 to 80° C., and reacted for 2 to 4 hours; after cooling to room temperature, the product is transferred to a rotary evaporator, tetrachloroethylene is removed by reduced pressure distillation, and 10 to 30 parts by mass of a fluorinated silicon polyether polyol is added thereto, and ultrasonic dispersion is performed for 1 to 2 hours to obtain a photothermal conversion modified nano slurry;

[0018] S2. Preparation of fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by photothermal conversion modified nano-slurry;

[0019] Add 75-90 parts by weight of fluorine-containing silicone polyether polyol and 10-25 parts by weight of the photothermal conversion modified nano slurry obtained in step S1 into a reaction container, vacuum dehydrate at 105-115° C. for 1-2 hours, add aliphatic or alicyclic diisocyanate after cooling to room temperature, react at 75-95° C. for 1-3 hours, then add a hydroxy diol compound containing a carboxylate group and a diol chain extender, the ratio of the amount of functional group substances in the above raw materials is -NCO / -OH=1.1-1.3, react at 75-85° C. for 2-4 hours, then add 100% of the amount of excess -NCO substance hydroxy acrylate monomer, continue to react for 1-3 hours, and obtain a polyurethane prepolymer with a carboxyl mass content of 1.0-2.5%;

[0020] The polyurethane prepolymer prepared above is cooled to room temperature, 20-40% of the mass of the polyurethane prepolymer perfluoroacrylate monomer is added, and then a neutralizing agent is added to neutralize the carboxylate groups therein into salts, with a neutralization degree of 80-110%;

[0021] The prepolymer is discharged into a disperser, and deionized water is added while stirring for dispersion, an initiator is added, and the temperature is raised to 70-90° C. for reaction for 2-4 hours, and the temperature is lowered to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicon waterborne polyurethane-fluorinated acrylate dispersion with a solid content of 50-60%;

[0022] S3. Preparation of micro-nano particle / fluorinated silane coupling agent modified slurry

[0023] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of micro-nano particles, 50 parts by mass of methanol and a mixed solution of 0.5-1.5 parts by mass of a fluorine-containing silane coupling agent are added, and the mixture is heated to 50-70° C. and refluxed for 12-24 hours; after cooling to room temperature, the product is transferred to a rotary evaporator, and the methanol is removed by reduced pressure distillation; ethanol is then added thereto, and ultrasonic dispersion is performed for 1-2 hours to obtain a micro-nano particle / fluorine-containing silane coupling agent modified slurry with a solid content of 15-30%;

[0024] S4. Preparation of photothermal conversion super-hydrophobic wind turbine blade surface protective coating

[0025] 100 parts by weight of the fluorinated silicone aqueous polyurethane-fluorinated acrylate dispersion modified by the photothermal conversion modified nano slurry prepared in step S2, 15 to 35 parts by weight of the micro-nanoparticle / fluorinated silane coupling agent modified slurry prepared in step S3, 1.0 to 2.0 parts by weight of a leveling agent, and 0.5 to 1.0 parts by weight of a defoaming agent are mixed, stirred evenly for later use, and 2.0 to 5.0 parts by weight of a curing agent are added before use to obtain a photothermal conversion super-hydrophobic wind turbine blade surface protective coating.

[0026] More preferably, the aforementioned photothermal conversion two-dimensional nanoparticles are one of nano-graphene, nano-boron nitride, and nano-MXene.

[0027] More preferably, the intercalant is one of hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, hexadecyltrimethylammonium chloride 1631, and octadecyltrimethylammonium chloride.

[0028] Further preferably, the aforementioned aliphatic or alicyclic diisocyanate is one or a mixture of hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate; the hydroxy diol compound containing a carboxylate group is one of 2,2-dihydroxymethylpropionic acid, 2,2-dihydroxymethylbutyric acid, and 2,2-dihydroxymethylhexanoic acid; and the diol chain extender is one of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0029] More preferably, the aforementioned hydroxy acrylate monomer is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; and the structural formula of the perfluoroacrylate monomer is: Where n is an integer ranging from 1 to 12.

[0030] Still further preferably, the initiator is one of potassium persulfate, ammonium persulfate, and sodium persulfate; the neutralizer is one of triethylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, and N-butyldiethanolamine; the micro-nano particles are one of micro-nano titanium dioxide, micro-nano silicon dioxide, and micro-nano kaolin; and the fluorine-containing silane coupling agent is one of heptadecafluorodecyltrimethoxysilane and tridecafluorooctyltriethoxysilane.

[0031] The present invention is beneficial in that:

[0032] (1) The coating of the present invention comprehensively considers the requirements of the photothermal conversion super-hydrophobic wind turbine blade surface protective coating for the surface of wind turbine blades, and uses a fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by a homemade photothermal conversion modified nano slurry as the main component. On the one hand, the dispersion effect of the photothermal conversion nano slurry is improved, and on the other hand, the evenly dispersed photothermal conversion nano particles ensure the photothermal conversion effect of the super-hydrophobic wind turbine blade surface protective coating, so that the moisture on the coating surface is easy to volatilize and difficult to freeze, and even if it freezes, it has the advantage of being easy to melt and drip;

[0033] (2) In the present invention, the micro-nano particles are modified by a fluorinated silane coupling agent to improve the dispersibility and stability of the micro-nano particles; the addition of a leveling agent and a defoaming agent effectively improves the construction performance of the fluorinated silicon waterborne polyurethane-based super-hydrophobic anti-icing coating for wind turbine blades; the preparation of the fluorinated silicon waterborne polyurethane dispersion and the introduction of the micro-nano particles / fluorinated silane coupling agent-modified slurry reduce the surface energy of the coating film after curing; under the action of the micro-nano particles modified by the fluorinated silane coupling agent, the fluorinated silicon waterborne polyurethane-based super-hydrophobic anti-icing coating for wind turbine blades presents a lotus leaf-like papillary structure, so that the coating achieves a super-hydrophobic effect;

[0034] (3) Compared with the wind turbine blade surface protective coatings currently on the market that have a single function and an inadequate anti-icing effect, the photothermal conversion super-hydrophobic wind turbine blade surface protective coating of the present invention has a particularly outstanding anti-icing effect, with ice adhesion as low as below 20 kPa; at the same time, the coating also has the advantages of being environmentally friendly, resistant to moisture and heat aging and ultraviolet aging, acid-resistant, and safe to use. DETAILED DESCRIPTION

[0035] The present invention is described in detail below with reference to specific embodiments.

[0036] Example 1

[0037] The preparation method of the photothermal conversion super-hydrophobic wind turbine blade surface protective coating of this embodiment is as follows:

[0038] S1. Preparation of photothermal conversion modified nano slurry

[0039] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of photothermal conversion two-dimensional nanographene particles, 20 parts by mass of tetrachloroethylene, 1 part by mass of hexadecyltrimethylammonium bromide and 0.5 parts by mass of isophorone diisocyanate were added, heated to 60°C, and reacted for 4 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and tetrachloroethylene was removed by reduced pressure distillation. Then 10 parts by mass of fluorinated silicone polyether polyol was added thereto, and ultrasonic dispersion was performed for 1 hour to obtain a photothermal conversion modified nano slurry.

[0040] S2, preparing a photothermal conversion modified nano-slurry modified fluorinated silicon waterborne polyurethane-fluorinated acrylate dispersion;

[0041] First, 90 parts by weight of fluorinated silicon polyether polyol and 10 parts by weight of the photothermal conversion modified nano slurry prepared in step S1 were added into a container, and vacuum dehydrated at 105° C. for 2 hours, cooled to room temperature, and 25 parts by weight of isophorone diisocyanate and 16 parts by weight of hexamethylene diisocyanate were added, and reacted at 75° C. for 3 hours, and then 5 parts by weight of 2,2-dimethylolpropionic acid and 4 parts by weight of ethylene glycol were added, and the reaction temperature was 85° C., and the reaction time was 2 hours. 17 parts by weight of hydroxyethyl acrylate was added, and the reaction was continued for 1 hour to obtain a polyurethane prepolymer;

[0042] The polyurethane prepolymer prepared above was cooled to room temperature, 23 parts by mass of perfluoroacrylate monomer (Formula 2) was added to reduce the viscosity, and then 3 parts by mass of triethylamine was added to neutralize and form a salt;

[0043]

[0044] The prepolymer was discharged into a disperser, 190 parts by mass of deionized water was added under stirring for dispersion, 1 part by mass of potassium persulfate was added, the temperature was raised to 70° C. for reaction for 4 hours, and the temperature was lowered to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion.

[0045] S3. Preparation of micro-nano particle / fluorinated silane coupling agent modified slurry

[0046] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of micro-nano titanium dioxide particles, 50 parts by mass of methanol and 0.5 parts by mass of a mixed solution of heptadecafluorodecyltrimethoxysilane were added, heated to 70°C, and refluxed for 12 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and the methanol was removed by reduced pressure distillation. 31 parts by mass of ethanol were added, and ultrasonic dispersion was performed for 1 hour to obtain a micro-nano particle / fluorinated silane coupling agent modified slurry.

[0047] S4. Preparation of photothermal conversion super-hydrophobic wind turbine blade surface protective coating and preparation method thereof

[0048] 100 parts by mass of the fluorinated silicone aqueous polyurethane-fluorinated acrylate dispersion modified by the photothermal conversion modified nano slurry prepared in step S2 were added, 35 parts by mass of the micro-nanoparticle / fluorinated silane coupling agent modified slurry prepared in step S3, 2.0 parts by mass of a polyorganosiloxane leveling agent, and 0.5 parts by mass of an aqueous organosilicon defoaming agent were added, and the mixture was stirred to uniformly mix the various additives for use. Before use, 2.0 parts by mass of a commercial waterborne polyurethane curing agent (UH 2593-1, Bayer) was added to obtain a photothermal conversion super-hydrophobic wind turbine blade surface protective coating.

[0049] Example 2

[0050] The preparation method of the photothermal conversion super-hydrophobic wind turbine blade surface protective coating of this embodiment is as follows:

[0051] S1. Preparation of photothermal conversion modified nano slurry

[0052] A mixed solution of 5 parts by mass of photothermal conversion two-dimensional nano boron nitride particles, 20 parts by mass of tetrachloroethylene, 1.5 parts by mass of dodecyl dimethyl benzyl ammonium chloride and 1.0 parts by mass of xylene diisocyanate was added to a four-necked flask equipped with a stirring device, a thermometer and a condenser, heated to 70°C, and reacted for 3 hours. After cooling to room temperature, the product was transferred to a rotary evaporator and tetrachloroethylene was removed by reduced pressure distillation. Then 20 parts by mass of fluorinated silicone polyether polyol was added and ultrasonically dispersed for 1.5 hours to obtain a photothermal conversion modified nano slurry.

[0053] S2. Preparation of photothermal conversion modified nano-slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion

[0054] First, add 85 parts by weight of fluorinated silicon polyether polyol and 15 parts by weight of the photothermal conversion modified nano slurry obtained in step S1 into a container, vacuum dehydrate at 110° C. for 1.5 hours, cool to room temperature, add 35 parts by weight of xylene diisocyanate, react at 85° C. for 2 hours, then add 8 parts by weight of 2,2-dihydroxymethylbutyric acid and 4 parts by weight of 1,4-butanediol, react at 80° C. for 3 hours, add 13 parts by weight of hydroxyethyl methacrylate, and continue to react for 2 hours to obtain a polyurethane prepolymer;

[0055] The polyurethane prepolymer prepared above was cooled to room temperature, 48 parts by weight of perfluoroacrylate monomer (Formula 3) was added to reduce the viscosity, and 6 parts by weight of N-methyldiethanolamine was added to neutralize the carboxylate therein to form a salt;

[0056]

[0057] The prepolymer was discharged into a disperser, 175 parts by mass of deionized water was added for dispersion under stirring, 1.5 parts by mass of sodium persulfate was added, the temperature was raised to 80° C. for reaction for 3 hours, and the temperature was lowered to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion.

[0058] S3. Preparation of micro-nano particle / fluorinated silane coupling agent modified slurry

[0059] A mixed solution of 5 parts by mass of micro-nano silica particles, 50 parts by mass of methanol and 1.0 parts by mass of tridecafluorooctyl triethoxysilane was added to a four-necked flask equipped with a stirring device, a thermometer and a condenser, heated to 60°C, and refluxed for 18 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and the methanol was removed by reduced pressure distillation; ethanol was added, and ultrasonic dispersion was performed for 1.5 hours to obtain a micro-nano particle / fluorinated silane coupling agent modified slurry with a solid content of 25%.

[0060] S4. Preparation of photothermal conversion super-hydrophobic wind turbine blade surface protective coating

[0061] 100 parts by mass of the fluorinated silicone aqueous polyurethane-fluorinated acrylate dispersion modified by the photothermal conversion modified nano slurry prepared in step S2 are added, and 25 parts by mass of the micro-nanoparticle / fluorinated silane coupling agent modified slurry prepared in step S3, 1.5 parts by mass of a polyether-modified polysiloxane leveling agent, and 0.8 parts by mass of an aqueous silicone defoamer are added, and the mixture is stirred to uniformly mix the various additives for later use. Before use, 4.0 parts by mass of a commercial aqueous polyurethane curing agent (DB82655, Wuhan Double Bond Company) is added to obtain a photothermal conversion super-hydrophobic wind turbine blade surface protective coating.

[0062] Example 3

[0063] The preparation method of the photothermal conversion super-hydrophobic wind turbine blade surface protective coating of this embodiment is as follows:

[0064] S1. Preparation of photothermal conversion modified nano slurry

[0065] A mixed solution of 5 parts by mass of photothermal conversion two-dimensional nano MXene particles, 20 parts by mass of tetrachloroethylene, 2 parts by mass of hexadecyltrimethylammonium chloride and 1.5 parts by mass of 4,4'-dicyclohexylmethane diisocyanate was added to a four-necked flask equipped with a stirring device, a thermometer and a condenser, heated to 80°C, and reacted for 2 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and tetrachloroethylene was removed by reduced pressure distillation. 30 parts by mass of fluorinated silicone polyether polyol was added, and ultrasonic dispersion was performed for 2 hours to obtain a photothermal conversion modified nano slurry.

[0066] S2. Preparation of photothermal conversion modified nano-slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion

[0067] First, add 75 parts by mass of fluorinated silicone polyether polyol and 25 parts by mass of the photothermal conversion modified nano slurry obtained in step S1 into a container, vacuum dehydrate at 115° C. for 1 hour, cool to room temperature, add 68 parts by mass of 4,4'-dicyclohexylmethane diisocyanate, react at 95° C. for 1 hour, then add 15 parts by mass of dimethylolpropionic acid and 2 parts by mass of 1,4-butanediol, react at 75° C. for 4 hours, add 20 parts by mass of hydroxypropyl methacrylate, and continue to react for 3 hours to obtain a polyurethane prepolymer;

[0068] The polyurethane prepolymer prepared above was cooled to room temperature, 82 parts by mass of perfluoroacrylate monomer (Formula 4) was added to reduce the viscosity, and 18 parts by mass of N-propyldiethanolamine was added to neutralize the carboxylate therein to form a salt;

[0069]

[0070] The prepolymer was discharged into a disperser, and 203 parts by mass of deionized water was added under stirring for dispersion. An initiator was added, and the temperature was raised to 90° C. for reaction for 2 hours. The temperature was cooled to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion.

[0071] S3. Preparation of micro-nano particle / fluorinated silane coupling agent modified slurry

[0072] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of micro-nano kaolin particles, 50 parts by mass of methanol and 1.5 parts by mass of a mixed solution of tridecafluorooctyl triethoxysilane were added, heated to 50°C, and refluxed for 24 hours. After cooling to room temperature, the product was transferred to a rotary evaporator and the methanol was removed by reduced pressure distillation. 15 parts by mass of ethanol was added and ultrasonically dispersed for 2 hours to obtain a micro-nano particle / fluorinated silane coupling agent modified slurry.

[0073] S4. Preparation of photothermal conversion super-hydrophobic wind turbine blade surface protective coating

[0074] 100 parts by mass of the fluorinated silicone aqueous polyurethane-fluorinated acrylate dispersion modified by the photothermal conversion modified nano slurry prepared in step S2 are added, and 15 parts by mass of the micro-nanoparticle / fluorinated silane coupling agent modified slurry prepared in step S3, 1.0 parts by mass of a fluorinated surfactant leveling agent, and 1.0 parts by mass of an aqueous silicone defoaming agent are added, and the mixture is stirred to uniformly mix the various additives for use. Before use, 5.0 parts by mass of a commercial waterborne polyurethane curing agent (2487, Bayer Covestro) is added to obtain a photothermal conversion super-hydrophobic wind turbine blade surface protective coating.

[0075] Comparative Example 1

[0076] The surface protective coating of this comparative example is a waterborne polyurethane-based wind turbine blade surface protective coating that is widely used in the market, and its preparation method is as follows:

[0077] S1. Preparation of waterborne polyurethane dispersion;

[0078] First, 100 parts by weight of polyether polyol was added to a container, vacuum-dehydrated at 105° C. for 2 hours, cooled to room temperature, 25 parts by weight of isophorone diisocyanate and 16 parts by weight of hexamethylene diisocyanate were added, and the mixture was reacted at 75° C. for 3 hours. Then, 4 parts by weight of dimethylolpropionic acid and 3 parts by weight of butanediol were added, and the reaction was continued at 75° C. for 4 hours. Then, 48 parts by weight of hydroxypropyl acrylate were added, and the reaction was continued for 3 hours to obtain a polyurethane prepolymer.

[0079] The polyurethane prepolymer prepared above was cooled to room temperature, and 3 parts by mass of triethanolamine was added to neutralize the carboxylate groups therein into salts;

[0080] The prepolymer was discharged into a disperser, and 299 parts by mass of deionized water was added under stirring for dispersion, thereby obtaining an aqueous polyurethane dispersion.

[0081] S2. Preparation of waterborne polyurethane-based wind turbine blade surface protective coating

[0082] 0.5 parts by mass of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 35 parts by mass of ethanol dispersion slurry of micro-nano titanium dioxide particles with a solid content of 15%, 1.0 parts by mass of polyorganosiloxane leveling agent and 0.5 parts by mass of water-based organosilicon defoaming agent were added to 100 parts by mass of the aqueous polyurethane dispersion prepared above, and the mixture was stirred to uniformly mix the various additives to obtain the aqueous polyurethane-based wind turbine blade surface protective coating of this comparative example.

[0083] Performance Testing

[0084] The coatings of Examples 1 to 3 and Comparative Example 1 were cured under ultraviolet light for 30 seconds and the performance tests were performed. The results were as follows:

[0085]

[0086] Table 1 Test results of Examples 1 to 3 and Comparative Example 1

[0087] It can be seen from the above table that after drying and curing, the coating of the present invention has good resistance to moisture and heat aging, resistance to ultraviolet aging and resistance to sulfuric acid corrosion, and the anti-icing performance and contact angle are significantly improved compared with Comparative Example 1. This is because the nano-slurry is modified by photothermal conversion. On the one hand, the dispersion effect of the photothermal conversion nano-slurry is improved, and on the other hand, the evenly dispersed photothermal conversion nano-particles ensure the photothermal conversion effect of the super-hydrophobic wind turbine blade surface protective coating coating; under the joint action of fluorine-containing silicone water-based polyurethane and fluorine-containing silane coupling agent modified micro-nanoparticles, the coating surface presents a lotus leaf-like papillary structure, so that the contact angle of the cured coating film is improved to more than 150°, thereby greatly reducing the adhesion between the wind turbine blade and the ice, which can well meet the needs of wind turbine blade anti-icing in cold areas.

[0088] In addition, the preparation method of the photothermal conversion super-hydrophobic wind turbine blade surface protective coating of the present invention is simple and easy to implement, the system has good compatibility, high production efficiency, easy industrialization, and very wide application. No toxic solvents are released during the entire process. It is a method for preparing a non-toxic, pollution-free, environmentally friendly coating and has excellent prospects for industrial promotion and application.

[0089] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the above embodiments do not limit the present invention in any form, and any technical solution obtained by equivalent replacement or equivalent transformation falls within the protection scope of the present invention.

Claims

1. A photothermal conversion super-hydrophobic wind turbine blade surface protective coating, characterized in that: It is compounded by the following components in parts by weight: 100 parts of fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by photothermal conversion nano slurry; 15-35 parts of micro-nano particle / fluorinated silane coupling agent modified slurry; 2~5 parts of curing agent; 1~2 parts of leveling agent; Defoaming agent 0.5~1 part; The photothermal conversion modified nano-slurry modified fluorinated silicon waterborne polyurethane-fluorinated acrylate dispersion is homemade, and the preparation method comprises the following steps: S1. Preparation of photothermal conversion modified nano-slurry A mixed solution of 5 parts by mass of photothermal conversion two-dimensional nanoparticles, 20 parts by mass of tetrachloroethylene, 1-2 parts by mass of an intercalant and 0.5-1.5 parts by mass of an aliphatic or alicyclic diisocyanate is added to a reaction container, heated to 60-80° C., and reacted for 2-4 hours; after cooling to room temperature, the product is transferred to a rotary evaporator, tetrachloroethylene is removed by reduced pressure distillation, and 10-30 parts by mass of a fluorinated silicon polyether polyol is added thereto, and ultrasonic dispersion is performed for 1-2 hours to obtain a photothermal conversion modified nano slurry; S2. Preparation of fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by photothermal conversion modified nano-slurry; Add 75-90 parts by weight of fluorinated silicone polyether polyol and 10-25 parts by weight of the photothermal conversion modified nano slurry obtained in step S1 into a reaction container, vacuum dehydrate at 105-115° C. for 1-2 hours, add aliphatic or alicyclic diisocyanate after cooling to room temperature, react at 75-95° C. for 1-3 hours, then add a hydroxy diol compound containing a carboxylate group and a diol chain extender, the ratio of the amount of functional group substances in the above raw materials is -NCO / -OH=1.1-1.3, react at 75-85° C. for 2-4 hours, then add 100% of the amount of hydroxy acrylate monomer of excess -NCO substance, continue to react for 1-3 hours, and obtain a polyurethane prepolymer with a carboxyl mass content of 1.0-2.5%; The polyurethane prepolymer prepared above is cooled to room temperature, 20-40% of the mass of the polyurethane prepolymer perfluoroacrylate monomer is added, and then a neutralizing agent is added to neutralize the carboxylate group therein into salt, and the neutralization degree is 80-110%; The prepolymer is discharged into a disperser, and deionized water is added while stirring for dispersion. An initiator is added, and the temperature is raised to 70-90°C for reaction for 2-4 hours. The temperature is cooled to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion with a solid content of 50-60%.

2. The photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 1, characterized in that: The curing agent is a commercial water-based polyurethane curing agent; the leveling agent is polyorganosiloxane, polyether-modified polyorganosiloxane or fluorine-containing surfactant; and the defoaming agent is a water-based organosilicon defoaming agent.

3. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 1, characterized in that: The steps include: S1. Preparation of photothermal conversion modified nano-slurry A mixed solution of 5 parts by mass of photothermal conversion two-dimensional nanoparticles, 20 parts by mass of tetrachloroethylene, 1-2 parts by mass of an intercalant and 0.5-1.5 parts by mass of an aliphatic or alicyclic diisocyanate is added to a reaction container, heated to 60-80° C., and reacted for 2-4 hours; after cooling to room temperature, the product is transferred to a rotary evaporator, tetrachloroethylene is removed by reduced pressure distillation, and 10-30 parts by mass of a fluorinated silicon polyether polyol is added thereto, and ultrasonic dispersion is performed for 1-2 hours to obtain a photothermal conversion modified nano slurry; S2. Preparation of fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion modified by photothermal conversion modified nano-slurry; Add 75-90 parts by weight of fluorinated silicone polyether polyol and 10-25 parts by weight of the photothermal conversion modified nano slurry obtained in step S1 into a reaction container, vacuum dehydrate at 105-115° C. for 1-2 hours, add aliphatic or alicyclic diisocyanate after cooling to room temperature, react at 75-95° C. for 1-3 hours, then add a hydroxy diol compound containing a carboxylate group and a diol chain extender, the ratio of the amount of functional group substances in the above raw materials is -NCO / -OH=1.1-1.3, react at 75-85° C. for 2-4 hours, then add 100% of the amount of hydroxy acrylate monomer of excess -NCO substance, continue to react for 1-3 hours, and obtain a polyurethane prepolymer with a carboxyl mass content of 1.0-2.5%; The polyurethane prepolymer prepared above is cooled to room temperature, 20-40% of the mass of the polyurethane prepolymer perfluoroacrylate monomer is added, and then a neutralizing agent is added to neutralize the carboxylate groups therein into salts, with a neutralization degree of 80-110%; The prepolymer is discharged into a disperser, and deionized water is added while stirring for dispersion, an initiator is added, and the temperature is raised to 70-90°C for reaction for 2-4 hours, and then the temperature is lowered to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicon waterborne polyurethane-fluorinated acrylate dispersion with a solid content of 50-60%. S3. Preparation of micro-nano particle / fluorinated silane coupling agent modified slurry In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of micro-nano particles, 50 parts by mass of methanol and a mixed solution of 0.5-1.5 parts by mass of a fluorinated silane coupling agent were added, and the mixture was heated to 50-70°C and refluxed for 12-24 hours; after cooling to room temperature, the product was transferred to a rotary evaporator, and the methanol was removed by reduced pressure distillation; ethanol was then added thereto, and ultrasonic dispersion was performed for 1-2 hours to obtain a micro-nano particle / fluorinated silane coupling agent modified slurry with a solid content of 15-30%; S4. Preparation of photothermal conversion super-hydrophobic wind turbine blade surface protective coating 100 parts by weight of the fluorinated silicone aqueous polyurethane-fluorinated acrylate dispersion modified by the photothermal conversion modified nano slurry prepared in step S2, 15 to 35 parts by weight of the micro-nanoparticle / fluorinated silane coupling agent modified slurry prepared in step S3, 1.0 to 2.0 parts by weight of a leveling agent, and 0.5 to 1.0 parts by weight of a defoaming agent are mixed, stirred evenly for later use, and 2.0 to 5.0 parts by weight of a curing agent are added before use to obtain a photothermal conversion super-hydrophobic wind turbine blade surface protective coating.

4. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The photothermal conversion two-dimensional nanoparticles are one of nano-graphene, nano-boron nitride and nano-MXene.

5. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The intercalant is one of hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, hexadecyltrimethylammonium chloride 1631, and octadecyltrimethylammonium chloride.

6. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The aliphatic or alicyclic diisocyanate is one or a mixture of hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate; the hydroxy diol compound containing a carboxylate group is one of 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolhexanoic acid; the diol chain extender is one of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

7. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The hydroxy acrylate monomer is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; the structural formula of the perfluoroacrylate monomer is: , where n is an integer ranging from 1 to 12.

8. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate; the neutralizer is one of triethylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine and N-butyldiethanolamine.

9. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The micro-nano particles are one of micro-nano titanium dioxide, micro-nano silicon dioxide and micro-nano kaolin.

10. The method for preparing a photothermal conversion super-hydrophobic wind turbine blade surface protective coating according to claim 3, characterized in that: The fluorine-containing silane coupling agent is one of heptadecafluorodecyltrimethoxysilane and tridecafluorooctyltriethoxysilane.

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