A lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades and its preparation method.

Abstract

This invention discloses a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades and its preparation method, belonging to the field of wind turbine blade technology. This high-conductivity heat storage and anti-icing film consists of heat-insulating fibers and a heat storage protective film arranged from the inside out on a blade substrate. The heat-insulating fibers are flexible organosilicon aerogel composite fibers, and the heat storage protective film is composed of hydrated salt / SiC composite phase change filler and water-based polyaspartic acid ester resin cross-linked by an adhesive coating. The heat storage protective film is on the outermost layer, where the hydrated salt acts as a phase change component, improving the heat storage performance of the coating. The heat-insulating fibers are positioned between the heat storage protective film and the wind turbine blade, employing a flexible organosilicon aerogel composite fiber layer for effective heat insulation. The wind turbine blade and the heat-insulating fibers, as well as the heat-insulating fibers and the heat storage protective film, are bonded together by an adhesive coating. The structure and composition of this protective film effectively absorb and store daytime solar heat within the coating, preventing icing of the wind turbine blade after the temperature drops at night.

Description

Technical Field

[0001] This invention belongs to the field of wind power generation technology, specifically relating to a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades and its preparation method. Background Technology

[0002] Wind power is a clean and renewable energy source, with its core equipment being the wind turbine. A wind turbine mainly consists of a tower, blades, a generator, and a control system. Among these, the blades are one of the most critical components, their design and material selection directly affecting the turbine's performance and lifespan. However, wind turbines are typically located in mountainous or border regions where there are significant diurnal temperature variations, making them prone to freezing. These areas often experience extreme weather events such as thunderstorms. During the day, these regions have ample sunlight and relatively high temperatures, but at night, temperatures drop below freezing, making the blade surfaces extremely susceptible to icing. Icing not only affects the blade's aerodynamic performance and reduces the turbine's power generation efficiency, but in severely iced areas, it can cause a power generation loss of approximately 20% to 50%. Lightning strikes can also damage the blades, affecting the turbine's normal operation and potentially leading to serious safety accidents. Therefore, enabling blades to withstand large temperature fluctuations and provide lightning protection is a pressing issue in the field of wind power technology. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a lightning protection, heat storage and anti-icing protective film suitable for the leading edge of wind turbine blades and its preparation method, so as to solve the problem that wind turbine blades are difficult to adapt to large environmental temperature differences and difficult to have lightning protection capabilities at the same time.

[0004] To achieve the above objectives, the present invention employs the following technical solution:

[0005] A method for preparing a lightning protection, heat storage and anti-icing protective film suitable for the leading edge of wind turbine blades. The preparation process is as follows: coating an adhesive coating on the blade substrate, then laying heat insulation fiber, then coating another layer of adhesive coating, placing a heat storage protective film on the adhesive coating, and obtaining an insulating, high-conductivity heat storage and anti-icing film after the adhesive coating dries.

[0006] The heat-insulating fiber is a flexible organosilicon aerogel composite fiber; the flexible organosilicon aerogel composite fiber is composed of organosilicon sol and hollow glass fiber;

[0007] The thermal storage protective film is composed of hydrated salt / SiC composite phase change filler and water-based polyaspartic acid ester resin crosslinked by an adhesive coating. The hydrated salt / SiC composite phase change filler is composed of eutectic hydrated salt and silicon carbide. The eutectic hydrated salt is composed of dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate.

[0008] The adhesive coating is a polyurethane-modified epoxy resin adhesive with modified nano-boron nitride added, wherein the modified nano-boron nitride is boron nitride encapsulated in polydopamine.

[0009] A further improvement of the present invention is that:

[0010] Preferably, the method for preparing the organosilicon aerogel is as follows:

[0011] (1) Mix silane, water, citric acid, urea and hexadecyltrimethylammonium chloride, stir and dissolve completely to obtain organosilicon sol;

[0012] (2) Pour the organosilicon sol into a mold containing hollow glass fibers. The organosilicon sol completely impregnates the hollow glass fibers. After oscillation aging, soak the oscillated aged material in water. After washing with isopropanol and n-hexane alternately, dry it at room temperature and pressure to obtain flexible organosilicon aerogel composite fiber.

[0013] Preferably, the silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane and vinyltrimethoxysilane in a molar ratio of 1:4:0.1:0.08:3.

[0014] Preferably, the preparation process of the adhesive coating is as follows: modified nano boron nitride is added during the preparation of component A of the polyurethane modified epoxy resin adhesive, and after mixing components A and B of the polyurethane modified epoxy resin adhesive, the mixture is stirred evenly to obtain the adhesive coating.

[0015] Preferably, the preparation process of the modified boron nanoparticles is as follows:

[0016] (1) Place the boron nitride raw material in water and stir at high speed to obtain a boron nitride suspension;

[0017] (2) Tris(hydroxymethyl)aminomethane was added to water to obtain a tris(hydroxymethyl)aminomethane buffer solution. The tris(hydroxymethyl)aminomethane buffer solution and boron nitride suspension were mixed and polydopamine was added. After stirring, NaOH was added to adjust the pH of the system to 8.5. After stirring, a mixed solution was obtained.

[0018] (3) After centrifuging the mixed solution obtained in step (2) several times, collect the precipitate in the lower layer each time and freeze-dry it to obtain boron nitride encapsulated with polydopamine, which is modified nano boron nitride.

[0019] Preferably, the preparation process of the adhesive thermal storage protective film is as follows:

[0020] Step 1: Mix the hydrated salt / SiC composite phase change filler and silane coupling agent KH550, then add toluene to obtain a mixed system; place the mixed system in a constant temperature oil bath vacuum filter pot, introduce nitrogen gas and stir. After the reaction is complete, perform vacuum filtration. After ultrasonic treatment, perform vacuum filtration again. Wash the filtered product with N,N-dimethylformamide and dry it to obtain the modified hydrated salt / SiC composite phase change filler micro powder.

[0021] Step 2: Mix the hydrated salt / SiC composite phase change filler micro powder and polyurethane prepolymer, add the chain extender and stir. After stirring, an insulating, high thermal conductivity and anti-icing dispersion is obtained.

[0022] Step 3: Add dispersant, titanium dioxide, carbon black, anti-settling agent, defoamer, leveling agent, light stabilizer, ultraviolet absorber and solvent to the insulating high thermal conductivity anti-icing dispersion in sequence, stir evenly and disperse to obtain coating A;

[0023] Step 3: Mix coating A and water-based isocyanate to obtain a heat storage coating;

[0024] Step 4: Vacuum inject the heat storage coating into the film-forming mold, and let it dry to obtain a heat storage protective film.

[0025] Preferably, in step 1, the preparation process of the hydrated salt / SiC composite phase change filler is as follows:

[0026] (1) Mix dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate and heat and stir to obtain a molten eutectic hydrated salt;

[0027] (2) Add insulating and thermally conductive filler silicon carbide to molten eutectic hydrated salt, and stir to obtain eutectic hydrated salt / SiC mixture;

[0028] (3) Add aluminum dihydrogen phosphate binder to the eutectic hydrated salt / SiC mixture to obtain a mixture;

[0029] (4) The mixture is dried and then sintered to obtain the sintered product;

[0030] (5) The sintered product was ball-milled to obtain a hydrated salt / SiC composite phase change filler.

[0031] Preferably, in step 2, the preparation process of the polyurethane prepolymer is as follows:

[0032] Dry polyether glycol is placed in a container, nitrogen gas is introduced into the container, and after stirring, the first catalyst and diisocyanate are added. After stirring, a hydrophilic chain extender is added, and the reaction is carried out. After the reaction product is cooled, a neutralizing agent is added to carry out a neutralization reaction to obtain polyurethane prepolymer.

[0033] Preferably, the hydrophilic chain extender is 2,2-dimethylolpropionic acid, dimethylolbutyric acid, or a mixture thereof;

[0034] The first catalyst is one or more of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide.

[0035] A lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades, prepared by any one of the above methods, comprises:

[0036] Thermal insulation fibers are installed on the outside of the wind turbine blades;

[0037] A heat storage protective film is installed outside the heat insulation fiber;

[0038] The heat insulation fiber and the wind turbine blade are bonded together by an adhesive coating, and the heat storage protective film and the heat insulation fiber are bonded together by an adhesive coating.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] This invention discloses a method for preparing a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades. The method involves placing heat-insulating fibers and a heat storage protective film on a blade substrate from the inside out. The heat-insulating fibers are flexible organosilicon aerogel composite fibers, and the heat storage protective film is composed of hydrated salt / SiC composite phase change filler and water-based polyaspartic acid ester resin cross-linked by an adhesive coating. The heat storage protective film is on the outermost layer, incorporating hydrated salt as a phase change component. This provides advantages such as high phase change enthalpy, high energy storage density, high thermal conductivity, and low cost, improving the heat storage performance of the coating. It can more effectively absorb and store daytime solar heat within the coating, preventing wind turbine blade icing and damage caused by nighttime temperature drops. Simultaneously, the selection of this material should consider its impact on blade performance and weight, thereby improving the efficiency of the wind turbine unit. The insulating fiber, positioned between the thermal storage protective membrane and the blades, utilizes a flexible silicone aerogel composite fiber layer. This layer not only effectively bonds to the substrate material (blade substrate) and fiberglass (epoxy resin material) but also provides limited thermal insulation. This allows the heat stored in the thermal storage protective membrane to remain largely within the membrane itself, minimizing heat loss. While protecting the blade substrate, it also keeps heat within the membrane, effectively absorbing heat during the day and allowing it to dissipate outwards at night. The insulating fiber and the thermal storage protective membrane are bonded together using an adhesive coating. This polyurethane-modified epoxy resin adhesive effectively connects the substrate and the thermal storage protective membrane, increasing adhesion. The adhesive coating also contains boron nitride encapsulated in polydopamine, further reducing the membrane's conductivity and improving its insulation performance.

[0041] Furthermore, the thermal storage protective film effectively utilizes the heat generated by sunlight during the day. When sunlight is strong, the heat is absorbed and quickly stored within the blade coating, preventing the wind turbine blades from being scorched by strong sunlight. At night, as temperatures drop, the coating quickly releases the heat, ensuring that the wind turbine blade surface does not freeze at lower nighttime temperatures. It also effectively prevents damage to the blades from lightning and ultraviolet radiation, improving the safety of the wind turbine unit. The thermal storage protective film uses silicon carbide as a thermal conductor and supporting material, which features high thermal conductivity, electrical insulation, and low cost. When temperatures drop at night, the stored heat can be quickly released to the blade surface, ensuring the blade's thermal stability and preventing icing. Silicon carbide has a thermal conductivity greater than 300 W / mK and a resistivity of 10⁵–10¹² Ω·cm at room temperature; it is not easily conductive and is classified as an insulating material. Furthermore, it does not chemically react with hydrated salts and possesses a certain degree of corrosion resistance. Its melting or decomposition temperature is higher than that of the phase change component, ensuring the shape stability and processability of the phase change component, thus enhancing the adhesion and reliability of the coating and maintaining good heat absorption and release effects even in harsh environments. This thermal storage protective film exhibits uniform and stable properties, without agglomeration or other issues, and does not increase the weight of the blades, thereby not affecting the efficiency of the wind turbine. The thermal storage coating of this invention is lighter and more suitable for use on wind turbine blades. The preparation process of the thermal storage protective film is simple, and the thermal storage cost is low. In areas with large diurnal temperature differences, it can reduce the costs of blade anti-icing and lightning protection, which is beneficial to improving the economic efficiency of wind power generation. Compared with existing technologies, the thermal storage coating of this invention is more economically valuable.

[0042] Furthermore, to ensure a consistent thickness of the thermal storage protective layer after construction on the blade surface, the material is prefabricated into a thermal storage protective film before construction. The film thickness can be adjusted according to the actual application conditions. The prefabricated film ensures uniform thickness, reducing construction difficulty and shortening construction time compared to paint application.

[0043] Furthermore, the thermal storage coating of the present invention can also provide additional protective functions, such as corrosion protection, thereby further improving the service life and performance of the blades.

[0044] Furthermore, compared to other films, the adhesive coating uses polyurethane-modified epoxy resin adhesive, which greatly enhances the bonding strength and prevents the film from falling off after a period of use.

[0045] Furthermore, adding modified boron nitride nanoparticles during the preparation of component A or component B of the polyurethane-modified epoxy resin adhesive can prevent the modified boron nitride nanoparticles from being difficult to disperse evenly and sufficiently during the preparation of the polyurethane-modified epoxy resin adhesive.

[0046] This invention also discloses a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades. The heat storage film includes heat-insulating fibers disposed outside the wind turbine blade and a heat storage protective film disposed outside the heat-insulating fibers. The heat-insulating fibers and the wind turbine blade are bonded together with an adhesive coating, and the heat storage protective film and the heat-insulating fibers are bonded together with the adhesive coating. The heat storage protective film can store daytime heat, solving the problem of high investment and maintenance costs compared to active de-icing technology, and does not rely on external heat for de-icing. This material embeds high thermal conductivity materials into a composite matrix, improving the thermal conductivity and thermal stability of the coating. While ensuring anti-icing, it protects the blade from being scorched by strong daytime sunlight without affecting the blade's performance and weight, thus improving the efficiency and stability of the wind turbine. Without increasing weight, it also ensures strong insulation of the blade, providing lightning protection. Using silane coupling agents as adhesive coatings, they can undergo covalent reactions with the surface of inorganic materials under certain conditions to form covalent bonds, thus firmly existing on the surface of inorganic materials. The amino groups on the other side can also undergo covalent reactions with the polymer matrix, enhancing the connection between the supporting material and the polymer matrix, and correspondingly improving the overall thermal conductivity of the coating.

[0047] Furthermore, the formulation of the thermal storage coating was optimized, lower-priced raw materials were selected, and the production process was simplified to reduce the manufacturing cost of the thermal storage coating.

[0048] Furthermore, the heat insulation fiber and the heat storage protection are bonded together by an adhesive coating. The fiber is a flexible silicone aerogel composite fiber, which utilizes the numerous cavities in the unique hollow structure of the aerogel to form a heat insulation layer to prevent heat conduction. Attached Figure Description

[0049] Figure 1 This is a schematic diagram of the insulating, high-conductivity, heat storage, and anti-icing membrane structure of the present invention. Detailed Implementation

[0050] The first aspect of this invention discloses a method for preparing a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades, comprising the following steps:

[0051] An adhesive coating is applied to the blade substrate, then thermal insulation fiber is laid, another layer of adhesive coating is applied, and finally a thermal storage protective film is bonded on top.

[0052] In some embodiments of the present invention, the blade substrate is sanded before the adhesive coating is applied, so that impurities are reduced on the surface of the blade substrate, and the adhesive coating can be better bonded to the blade surface.

[0053] In some embodiments of the present invention, the adhesive coating is an epoxy resin coating, more specifically a polyurethane modified epoxy resin adhesive, wherein modified nano boron nitride is added; polyurethane elastic molecules are introduced into the epoxy resin, and under the action of curing agent and catalyst, the two can form an interpenetrating network system IPN, which effectively improves the strength and deformation capacity of the epoxy system and can act as a bridge between the epoxy resin substrate and the polyurethane system heat storage protective film.

[0054] Polyurethane modified epoxy resin adhesives consist of epoxy resin, polyurethane prepolymer (or toughening agent), curing agent, accelerator, filler, and other possible additives.

[0055] Specifically, the preparation process of polyurethane with modified nano boron nitride is as follows: epoxy resin, filler and other raw materials are mixed evenly according to the formula as component A, curing agent, accelerator and other raw materials are mixed evenly as component B, components A, B and toughening agent are mixed evenly in a certain proportion, and after stirring evenly, polyurethane modified epoxy resin adhesive can be made. It is necessary to avoid mixing components A and B in advance to avoid premature curing. In the process of preparing component A, a set amount of modified nano boron nitride polyurethane can be added, and finally a polyurethane modified epoxy resin adhesive with modified nano boron nitride is formed.

[0056] As a preferred embodiment, the amount of modified boron nitride nanoparticles added to the polyurethane-modified epoxy resin adhesive is 3-5 wt% of its mass, and the modified boron nitride nanoparticles are polydopamine-encapsulated boron nitride. This material utilizes polydopamine to encapsulate the boron nitride, forming a polydopamine film on the surface of the boron nitride material to promote the dispersion of the boron nitride material in the epoxy resin and improve the interfacial compatibility between boron nitride and the epoxy resin.

[0057] The specific preparation process of modified boron nitride nanoparticles is as follows:

[0058] Step 1: Weigh the boron nitride raw material and add it to deionized water. Stir the mixture at 12000-15000 rpm for 8-10 minutes using a high-speed mixer to form a boron nitride suspension with a concentration of 100 g / mL.

[0059] Step 2: Prepare a 0.06 mol / L buffer solution by adding tris(hydroxymethyl)aminomethane to deionized water, add boron nitride suspension that has been stirred, then add polydopamine, mix and stir at 700 rpm, add NaOH powder to adjust the pH to 8.5, and stir the resulting solution at 700 rpm for 24 h to obtain a mixed solution; wherein the volume ratio of tris(hydroxymethyl)aminomethane buffer solution to boron nitride suspension is 4:1, and the concentration of polydopamine in the mixed solution is 7.5 g / L.

[0060] Step 3: Centrifuge the solution obtained in Step 2 at 7000 rpm 10 times, and perform lower layer precipitation each time. Freeze-dry the obtained powder for 24 hours to obtain polydopamine-encapsulated boron nitride (BN-HPDA).

[0061] In some embodiments of the present invention, the heat-insulating fiber is a flexible organosilicon aerogel composite fiber. Combining the heat-resistant properties of traditional organosilicon resin ablation and the excellent heat-insulating properties of aerogel, an organosilicon aerogel composite fiber material is prepared.

[0062] The specific preparation method includes the following steps:

[0063] Step 1: Mix silane, water, citric acid, urea, and hexadecyltrimethylammonium chloride uniformly in a molar ratio of 1:4:0.1:0.08:3. The silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane, and vinyltrimethoxysilane in a molar ratio of 3:5:2.4. After complete dissolution, stir vigorously for 0.5 to 1 hour to obtain organosilicon sol.

[0064] Step 2: Pour the silicone sol into a mold containing hollow glass fibers of a predetermined size, ensuring complete impregnation of the fibers. Allow the sol to gel and age at 80°C for 24 hours using a vibration method. Then, soak the fibers in 60°C water for 24 hours, followed by two alternating washes with 60°C isopropanol and n-hexane solutions, with an 8-hour interval between each wash. Finally, dry the fibers at room temperature and pressure for 72 hours to obtain flexible silicone aerogel composite fibers. The resulting flexible silicone aerogel composite material is a soft solid material; its specific thickness and dimensions can be adjusted by modifying the mold dimensions.

[0065] In some embodiments of the present invention, a method for preparing a thermal storage protective film is also disclosed. This method uses dipotassium hydrogen phosphate hexahydrate as the phase change matrix, disodium hydrogen phosphate dodecahydrate as the nucleating agent, silicon carbide as the thermal conductor and supporting material, and waterborne polyaspartic acid ester resin. Specifically, dipotassium hydrogen phosphate hexahydrate, disodium hydrogen phosphate dodecahydrate, and glycine are used to prepare a eutectic hydrated salt. A mixed sintering method is then used to prepare the hydrated eutectic salt / SiC phase change filler. This hydrated eutectic salt / SiC is crosslinked and mixed with the waterborne polyaspartic acid ester resin using a binder to form a thermal storage coating. The method for preparing this thermal storage protective film includes the following steps:

[0066] Step 1, Preparation of hydrated salt phase change materials

[0067] Dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate were mixed in a beaker at a mass ratio of 176.67:13.86:0.99. The mixture was then heated and stirred in a water bath at 55°C until it melted into a transparent liquid, thus obtaining a molten eutectic hydrated salt.

[0068] Step 2, Preparation of hydrated salt / SiC composite phase change thermal storage material

[0069] (1) Add insulating and thermally conductive silicon carbide filler to the molten eutectic hydrated salt in step 1. After mechanical stirring for 10-15 min, a eutectic hydrated salt / SiC mixture is obtained. The stirring speed is 60-110 r / min, and the silicon carbide particle size is 2-5 μm.

[0070] The mass fraction of silicon carbide is 50% to 80% of the mass of the eutectic hydrate salt.

[0071] (2) The eutectic hydrated salt / SiC mixture after thorough and uniform mixing is placed into a crucible and an appropriate amount of aluminum dihydrogen phosphate binder is added.

[0072] The aluminum dihydrogen phosphate content is 3-4.5% of the mass of the eutectic hydrate salt / SiC mixture. In this process, aluminum dihydrogen phosphate acts as a binder, which can bind SiC and eutectic salt particles together.

[0073] (3) Place the crucible from step (2) into a drying oven at 120°C for 4 to 6 hours to pre-dry it. Then close the drying oven and let it cool naturally to room temperature before taking it out.

[0074] (4) Take out the crucible after cooling in step (3) and sinter it using a specific heating program.

[0075] The heating program is as follows: heating from 0 to 25°C for 40 minutes and holding for 20 minutes; within 40 minutes, heating from 25°C to 50°C and holding at 50°C for 20 minutes; within 40 minutes, heating from 50°C to 75°C and holding at 75°C for 20 minutes; within 30 minutes, heating from 75°C to 100°C and holding at 100°C for 30 minutes; and holding at the highest sintering temperature of 100°C for 1 hour.

[0076] It should be noted that during the heating process described above, if the temperature of process mixture B itself is high after it is removed, there is no need to perform a heating process from 0 to 25°C; the temperature can be increased directly within the subsequent temperature range.

[0077] (5) After the heat preservation process in step (4) is completed, take out the mixture in the crucible and put it into a planetary ball mill. Dry grind the mixture at a ball-to-material ratio of 1:1 and a speed of 100r / min until the particle size of the mixture is 10-20μm to obtain hydrated salt / SiC composite phase change filler.

[0078] Step 3: Weigh the base material of the water-soluble polyaspartic acid ester resin.

[0079] The base materials of waterborne polyaspartic acid ester resin include: diisocyanate, polyether glycol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent.

[0080] Specifically, the diisocyanate is any one or a mixture of isoflurone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, and its mass content is 20-25% of the polyurethane base material.

[0081] Specifically, the polyether glycol is one or more of polytetrahydrofuran glycol (PTMG), polyethylene glycol, and polypropylene glycol, and its mass content is 15-20% of the polyurethane base material.

[0082] Specifically, the chain extender is 1,5-pentanediol, and its mass content is 2.5% to 7.5% of the polyurethane base material;

[0083] Specifically, the hydrophilic chain extender is one or a mixture of two of 2,2-dimethylolpropionic acid and dimethylolbutyric acid, and its mass content is 1-2% of the polyurethane base material;

[0084] Specifically, the first catalyst is one or more of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide, and its mass content is 1 to 3.5% of the polyurethane base material;

[0085] Specifically, the neutralizing agent is one or more of triethylamine, tripropylamine, formic acid, acetic acid, and triethanolamine, and its mass content is 0.5% to 2% of the polyurethane base material.

[0086] Specifically, the solvent is N,N-dimethylformamide, and its mass content is 50% of the polyurethane base material.

[0087] It should be understood that the polyurethane base material mentioned above is the composition and corresponding material of the final waterborne polyaspartic ester resin. A portion of it is used in the next step to prepare the polyurethane prepolymer, and a portion is added in the final preparation step.

[0088] Step 4: Prepare polyurethane prepolymer

[0089] (1) Weigh the diisocyanate, polyether glycol, hydrophilic chain extender, first catalyst and neutralizer according to the set mass ratio;

[0090] (2) Dry the weighed polyether glycol at 110°C for 5 hours.

[0091] (3) Take out the dried polyether glycol from step (2) and put it into a three-necked round bottom flask. Pour nitrogen into the flask and start stirring. The stirring conditions are: 350 r / min, 20 min.

[0092] (4) Add the weighed first catalyst and diisocyanate to the flask in step (3), and start stirring. The stirring conditions are: 350 r / min, 88℃, 30-60 min.

[0093] (5) Add the weighed hydrophilic chain extender to the flask in step (4), turn on the stirrer, and the stirring conditions are: 350 r / min, 80℃, 2-3 h;

[0094] (6) Cool the reaction product of step (5) to 50°C, add the weighed neutralizing agent to carry out the neutralization reaction for 30 to 40 minutes to obtain polyurethane prepolymer.

[0095] Step 5, Preparation of Insulating, High Thermal Conductivity, and Anti-icing Coating

[0096] (1) Add the hydrated salt / SiC composite phase change filler powder and silane coupling agent KH550 to a three-necked flask at a molar ratio of 25:1, and add toluene as a solvent for the reaction environment.

[0097] (2) Place the three-necked flask in a constant temperature oil bath, heat it to 90°C, introduce nitrogen gas and maintain the nitrogen atmosphere, start stirring and react for 6 hours at a stirring speed of 100-150 r / min.

[0098] (3) After the reaction is complete, the mixed solution in (2) is vacuum filtered.

[0099] (4) After vacuum filtration, pour the hydrated salt / SiC composite phase change filler powder into a beaker, add deionized water, and sonicate for 30-60 minutes. After sonication, filter again.

[0100] (5) Add N,N-dimethylformamide to the hydrated salt / SiC composite phase change filler powder after filtration in (4) and wash it twice.

[0101] (6) Place the cleaned hydrated salt / SiC composite phase change filler powder from (5) into a vacuum drying oven; the drying oven needs to be preheated to 105℃ and kept at a constant temperature for 12 hours to obtain the modified hydrated salt / SiC composite phase change filler powder.

[0102] (7) Cool the reaction product of step (6) to 35°C and add it to the polyurethane prepolymer at a mass content of 30-60%.

[0103] (8) Add the weighed chain extender and solvent to (7) and start stirring. The stirring conditions are 900-2000 r / min for 30-60 min. Finally, an insulating, high thermal conductivity, and anti-icing dispersion is obtained.

[0104] (9) Add the following to the dispersion obtained in step (8) in sequence: dispersant (1% to 1.5% of the total mass fraction of component A, acrylic dispersant), titanium dioxide (25% to 30% of component A, filler for color adjustment), carbon black (0.05% to 0.1% of component A, for color adjustment and to enhance light absorption), anti-settling agent (0.5% to 1% of component A, nano-silica or polyamide wax), defoamer (0.5% to 1%), leveling agent (0.8% to 1%), light stabilizer (0.5% to 1%, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidine) sebacate and 1-methyl-8-(1,2,2,6,6-pentamethyl-4-piperidine) sebacate), ultraviolet absorber (0.8% to 1.2%, hydroxyphenylbenzotriazole ultraviolet absorber), and solvent (propylene glycol methyl ether acetate, dimethyl sulfoxide, xylene, 3% to 10%). After mixing thoroughly with stirring at low speed, disperse at high speed at 2500 rpm / min, maintaining a temperature above 40 degrees Celsius for at least 30 minutes, and check the fineness to be no higher than 50 μm to form coating A.

[0105] In component A of the coating, the remainder, by mass fraction, is a dispersion, excluding the dispersant, titanium dioxide, carbon black, anti-settling agent, defoamer, leveling agent, light stabilizer, UV absorber, and solvent mentioned above.

[0106] (10) Weigh the water-based isocyanate (component B) according to the weight of the modified dispersion of the reaction product in step (8). The ratio of the two is calculated as n(—NCO):n(—NH)=1.2:1. Before use, component A and component B can be stirred thoroughly and mixed evenly to finally obtain the heat storage coating.

[0107] (11) Vacuum inject the heat storage coating into the film forming mold. The bottom material of the mold is polytetrafluoroethylene material, which is non-adhesive. The injection thickness is controlled between 200μm and 500μm. After 24 hours, it can be peeled off to obtain the finished heat storage film.

[0108] The following description, in conjunction with specific embodiments, provides further details.

[0109] Example 1

[0110] Step 1, prepare the adhesive coating;

[0111] The adhesive coating consists of component A, which includes epoxy resin E-44 and filler; and component B, which includes curing agent I, polyamide 650, DMP, and toughening agent.

[0112] Component A is obtained by mixing epoxy resin E-44, filler and modified nano boron nitride. Component B is obtained by mixing curing agent I, polyamide 650 and DMP. The adhesive coating is obtained by mixing and stirring components A, B and toughening agent. The amount of modified nano boron nitride is 3 wt% of the total mass of the adhesive coating.

[0113] Step 2, prepare the heat-insulating fiber;

[0114] (1) Silane, water, citric acid, urea and hexadecyltrimethylammonium chloride are mixed evenly, wherein the silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane and vinyltrimethoxysilane in a molar ratio of 3:5:2.4. After complete dissolution, the mixture is stirred vigorously for 1 hour to obtain organosilicon sol.

[0115] (2) The organosilicon sol was poured into a mold containing hollow glass fibers of the same size, allowing the fibers to be completely impregnated. The mixture was then aged by gel vibration at 80°C for 24 hours, followed by soaking in water at 60°C for 24 hours. Next, it was washed twice alternately with isopropanol and n-hexane solutions at 60°C, with an 8-hour interval between each wash. Finally, it was dried at room temperature and pressure for 72 hours to obtain flexible organosilicon aerogel composite fibers. The obtained flexible organosilicon aerogel composite material is a soft solid material, and its specific thickness and dimensions can be adjusted by changing the size of the mold.

[0116] Step 3, Prepare the heat storage protective film

[0117] Step 3.1, Preparation of hydrated salt phase change materials

[0118] Dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate were mixed in a beaker at a mass ratio of 176.67:13.86 and heated and stirred in a water bath at 55°C until they melted into a transparent liquid, thus obtaining a molten eutectic hydrated salt.

[0119] Step 3.2, Preparation of hydrated salt / SiC composite phase change thermal storage material

[0120] (1) Add insulating and thermally conductive silicon carbide filler to the molten eutectic hydrated salt obtained in step 3.1. After mechanical stirring for 12 min, a eutectic hydrated salt / SiC mixture is obtained. The stirring speed is 80 r / min, and the silicon carbide particle size is 2-5 μm.

[0121] The mass fraction of silicon carbide is 60% of the mass of the eutectic hydrate salt.

[0122] (2) The eutectic hydrated salt / SiC mixture after being thoroughly and uniformly mixed is loaded into a crucible, and an appropriate amount of aluminum dihydrogen phosphate binder is added to obtain process mixture A.

[0123] The aluminum dihydrogen phosphate content is 4% of the mass of the eutectic hydrate salt / SiC mixture.

[0124] (3) Place the process mixture A obtained in step (2) into a crucible, put the crucible into a drying oven at 120°C and dry for 5 hours. Then close the drying oven and let it cool naturally to room temperature before taking it out to obtain process mixture B.

[0125] (4) Take out the cooled process mixture B and sinter it with a specific heating program to obtain process mixture C;

[0126] The heating process is as follows: heat from room temperature to 30°C for 40 minutes and hold for 20 minutes; heat to 60°C for 40 minutes and hold for 20 minutes; heat to 90°C for 30 minutes and hold for 30 minutes; and hold at the highest sintering temperature of 100°C for 1 hour.

[0127] (5) After the heat preservation process in step (4) is completed, take out the process mixture C in the crucible and put it into a planetary ball mill. Dry grind the mixture at a ball-to-material ratio of 1:1 and a speed of 100r / min until the particle size of the mixture is 10-20μm to obtain the hydrated salt / SiC composite phase change filler.

[0128] Step 3.3, Weigh the polyurethane base material

[0129] Specifically, the diisocyanate is isoflurone diisocyanate, and its mass content is 22% of the polyurethane base material;

[0130] Specifically, the polyether diol is polytetrahydrofuran diol, and its mass content is 18% of the polyurethane prepolymer;

[0131] Specifically, the chain extender is 1,5-pentanediol, and its mass content is 5% of the polyurethane prepolymer;

[0132] Specifically, the hydrophilic chain extender is 2,2-dimethylolpropionic acid, and its mass content is 1.5% of the polyurethane prepolymer;

[0133] Specifically, the catalyst is dibutyltin dilaurate, and its mass content is 2% of the polyurethane prepolymer;

[0134] Specifically, the neutralizing agent is a type of triethylamine, and its mass content is 1.5% of the polyurethane prepolymer.

[0135] Specifically, the solvent is N,N-dimethylformamide, and its mass content is 50% of that of the polyurethane prepolymer.

[0136] Step 3.4, Preparation of polyurethane prepolymer

[0137] (1) Weigh the diisocyanate, polyether glycol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent according to the set mass ratio;

[0138] (2) Dry the weighed polyether glycol at 110°C for 5 hours.

[0139] (3) Take out the dried polyether diol from step (2) and put it into a three-necked round bottom flask. Pour nitrogen into the flask and start stirring. The stirring speed is 350 r / min and the stirring time is 20 min.

[0140] (4) Add the weighed catalyst and diisocyanate to the flask in step (3), start stirring, the stirring speed is 350 r / min, the stirring temperature is 88℃, and the stirring time is 50 min.

[0141] (5) Add the weighed hydrophilic chain extender to the flask in step (4), turn on the stirrer, the stirring speed is 350 r / min, the stirring temperature is 80℃, and the stirring time is 2.5 h.

[0142] (6) Cool the reaction product of step (5) to 50°C, add the weighed neutralizing agent to carry out the neutralization reaction for 35 minutes to obtain polyurethane prepolymer.

[0143] Step 3.5, Preparation of modified hydrated salt / SiC composite phase change filler micro powder

[0144] (1) Add the hydrated salt / SiC composite phase change filler and silane coupling agent KH550 to a three-necked flask in a ratio of 25:1, and add toluene as a solvent for the reaction environment.

[0145] (2) Place the three-necked flask in a constant temperature oil bath, heat it to 90°C, introduce nitrogen gas and maintain the nitrogen atmosphere, start stirring and react for 6 hours at a stirring speed of 120 r / min.

[0146] (3) After the reaction is complete, the mixed solution in (2) is vacuum filtered.

[0147] (4) After vacuum filtration, pour the hydrated salt / SiC composite phase change filler powder into a beaker, add deionized water, and sonicate for 40 minutes. After sonication, filter again.

[0148] (5) Add N,N-dimethylformamide to the hydrated salt / SiC composite phase change filler powder after filtration in (4) and wash it twice.

[0149] (6) Place the cleaned hydrated salt / SiC composite phase change filler powder from (5) into a vacuum drying oven; the drying oven needs to be preheated to 105℃ and kept at a constant temperature for 12 hours. The modified hydrated salt / SiC composite phase change filler powder is obtained.

[0150] Step 3.6: Prepare an insulating, high thermal conductivity, and anti-icing coating.

[0151] (1) Cool the reaction product of step 3.5 to 35°C and add it to the polyurethane prepolymer at 40% of the mass content of the polyurethane prepolymer to obtain a mixture.

[0152] (2) Add the weighed chain extender and solvent to the mixture obtained in the previous step, and start stirring. The stirring conditions are 1500 r / min for 40 min, and finally the insulating, high thermal conductivity and anti-icing coating is obtained.

[0153] Example 2

[0154] Step 1, prepare the adhesive coating;

[0155] The adhesive coating consists of component A, which includes epoxy resin E-44 and filler; and component B, which includes curing agent I, polyamide 650, DMP, and toughening agent.

[0156] Component A is obtained by mixing epoxy resin E-44, filler and modified nano boron nitride. Component B is obtained by mixing curing agent I, polyamide 650 and DMP. The adhesive coating is obtained by mixing and stirring components A, B and toughening agent. The amount of modified nano boron nitride is 4 wt% of the total mass of the adhesive coating.

[0157] Step 2, prepare the heat-insulating fiber;

[0158] (1) Silane, water, citric acid, urea and hexadecyltrimethylammonium chloride are mixed evenly, wherein the silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane and vinyltrimethoxysilane in a molar ratio of 3:5:2.4. After complete dissolution, the mixture is stirred vigorously for 1 hour to obtain organosilicon sol.

[0159] (2) The organosilicon sol was poured into a mold containing hollow glass fibers of the same size, allowing the fibers to be completely impregnated. The mixture was then aged by gel vibration at 80°C for 24 hours, followed by soaking in water at 60°C for 24 hours. Next, it was washed twice alternately with isopropanol and n-hexane solutions at 60°C, with an 8-hour interval between each wash. Finally, it was dried at room temperature and pressure for 72 hours to obtain flexible organosilicon aerogel composite fibers. The obtained flexible organosilicon aerogel composite material is a soft solid material, and its specific thickness and dimensions can be adjusted by changing the size of the mold.

[0160] Step 3, Prepare the heat storage protective film

[0161] Step 3.1, Preparation of hydrated salt phase change materials

[0162] Dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate were mixed in a beaker at a mass ratio of 176.67:13.86, and heated and stirred in a water bath at 55°C until they melted into a transparent liquid to obtain a eutectic hydrated salt.

[0163] Step 3.2, Preparation of hydrated salt / SiC composite phase change thermal storage material

[0164] (1) Add insulating and thermally conductive silicon carbide filler to the molten eutectic hydrated salt obtained in step 1. After mechanical stirring for 10 min, a eutectic hydrated salt / SiC mixture is obtained. The stirring speed is 110 r / min, and the silicon carbide particle size is 2-5 μm.

[0165] The mass fraction of silicon carbide is 50% of the mass of the eutectic hydrate salt.

[0166] (2) The eutectic hydrated salt / SiC mixture after being thoroughly and uniformly mixed is loaded into a crucible, and an appropriate amount of aluminum dihydrogen phosphate binder is added to obtain process mixture A.

[0167] The aluminum dihydrogen phosphate content is 3% of the mass of the eutectic hydrated salt / SiC mixture.

[0168] (3) Place the process mixture A obtained in step (3) into a crucible, put the crucible into a drying oven at 120°C and dry for 4 hours. Then close the drying oven and let it cool naturally to room temperature before taking it out to obtain process mixture B.

[0169] (4) Take out the cooled process mixture B and sinter it with a specific heating program to obtain process mixture C;

[0170] The heating process is as follows: heat from room temperature to 25°C for 40 minutes and hold for 20 minutes; heat to 50°C for 40 minutes and hold for 20 minutes; heat to 75°C for 30 minutes and hold for 30 minutes; and hold at the highest sintering temperature of 100°C for 1 hour.

[0171] (5) After the heat preservation process in step (4) is completed, take out the process mixture C in the crucible and put it into a planetary ball mill. Dry grind the mixture at a ball-to-material ratio of 1:1 and a speed of 100r / min until the particle size of the mixture is 10-20μm to obtain the hydrated salt / SiC composite phase change filler.

[0172] Step 3.3, Weigh the polyurethane base material

[0173] Specifically, the diisocyanate is hexamethylene diisocyanate, and its mass content is 20% of the polyurethane base material;

[0174] Specifically, the polyether glycol is polyethylene glycol, and its mass content is 20% of the polyurethane prepolymer;

[0175] Specifically, the chain extender is 1,5-pentanediol, and its mass content is 4% of the polyurethane prepolymer;

[0176] Specifically, the hydrophilic chain extender is dimethylolbutyric acid, and its mass content is 2% of the polyurethane prepolymer;

[0177] Specifically, the catalyst is stannous octoate, and its mass content is 2% of the polyurethane prepolymer;

[0178] Specifically, the neutralizing agent is formic acid, and its mass content is 2% of the polyurethane prepolymer.

[0179] Specifically, the solvent is N,N-dimethylformamide, and its mass content is 50% of that of the polyurethane prepolymer.

[0180] Step 3.4, Preparation of polyurethane prepolymer

[0181] (1) Weigh the diisocyanate, polyether glycol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent according to the set mass ratio;

[0182] (2) Dry the weighed polyether glycol at 110°C for 5 hours.

[0183] (3) Take out the dried polyether diol from step (2) and put it into a three-necked round bottom flask. Pour nitrogen into the flask and start stirring. The stirring speed is 350 r / min and the stirring time is 20 min.

[0184] (4) Add the weighed catalyst and diisocyanate to the flask in step (3), start stirring, the stirring speed is 350 r / min, the stirring temperature is 88℃, and the stirring time is 30 min.

[0185] (5) Add the weighed hydrophilic chain extender to the flask in step (4), turn on the stirrer, the stirring speed is 350 r / min, the stirring temperature is 80℃, and the stirring time is 2h.

[0186] (6) Cool the reaction product of step (5) to 50°C, add the weighed neutralizing agent to carry out the neutralization reaction for 30 minutes to obtain polyurethane prepolymer.

[0187] Step 3.5, Preparation of modified hydrated salt / SiC composite phase change filler micro powder

[0188] (1) Add the hydrated salt / SiC composite phase change filler and silane coupling agent KH550 to a three-necked flask in a ratio of 25:1, and add toluene as a solvent for the reaction environment.

[0189] (2) Place the three-necked flask in a constant temperature oil bath, heat it to 90°C, introduce nitrogen gas and maintain the nitrogen atmosphere, start stirring and react for 6 hours at a stirring speed of 100 r / min.

[0190] (3) After the reaction is complete, the mixed solution in (2) is vacuum filtered.

[0191] (4) After vacuum filtration, pour the hydrated salt / SiC composite phase change filler powder into a beaker, add deionized water, and sonicate for 30 minutes. After sonication, filter again.

[0192] (5) Add N,N-dimethylformamide to the hydrated salt / SiC composite phase change filler powder after filtration in (4) and wash it twice.

[0193] (6) Place the cleaned hydrated salt / SiC composite phase change filler powder from (5) into a vacuum drying oven; the drying oven needs to be preheated to 105℃ and kept at a constant temperature for 12 hours. The modified hydrated salt / SiC composite phase change filler powder is obtained.

[0194] Step 3.6: Prepare an insulating, high thermal conductivity, and anti-icing coating.

[0195] (1) Cool the reaction product of step 4 to 35°C and add it to the polyurethane prepolymer at 40% of the mass content of the polyurethane prepolymer.

[0196] (2) Add the weighed chain extender and solvent to (7) and start stirring. The stirring conditions are 900 r / min and 60 min. Finally, the insulating, high thermal conductivity and anti-icing coating is obtained.

[0197] Example 3

[0198] Step 1, prepare the adhesive coating;

[0199] The adhesive coating consists of component A, which includes epoxy resin E-44 and filler; and component B, which includes curing agent I, polyamide 650, DMP, and toughening agent.

[0200] Component A is obtained by mixing epoxy resin E-44, filler and modified nano boron nitride. Component B is obtained by mixing curing agent I, polyamide 650 and DMP. The adhesive coating is obtained by mixing and stirring components A, B and toughening agent. The amount of modified nano boron nitride is 5 wt% of the total mass of the adhesive coating.

[0201] Step 2, prepare the heat-insulating fiber;

[0202] (1) Silane, water, citric acid, urea and hexadecyltrimethylammonium chloride are mixed evenly, wherein the silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane and vinyltrimethoxysilane in a molar ratio of 3:5:2.4. After complete dissolution, the mixture is stirred vigorously for 1 hour to obtain organosilicon sol.

[0203] (2) The organosilicon sol was poured into a mold containing hollow glass fibers of the same size, allowing the fibers to be completely impregnated. The mixture was then aged by gel vibration at 80°C for 24 hours, followed by soaking in water at 60°C for 24 hours. Next, it was washed twice alternately with isopropanol and n-hexane solutions at 60°C, with an 8-hour interval between each wash. Finally, it was dried at room temperature and pressure for 72 hours to obtain flexible organosilicon aerogel composite fibers. The obtained flexible organosilicon aerogel composite material is a soft solid material, and its specific thickness and dimensions can be adjusted by changing the size of the mold.

[0204] Step 3, Prepare the heat storage protective film

[0205] Step 3.1, Preparation of hydrated salt phase change materials

[0206] Dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate were mixed in a beaker at a mass ratio of 176.67:13.86, and then heated and stirred in a water bath at 55°C until they melted into a transparent liquid, thus obtaining a molten eutectic hydrated salt.

[0207] Step 3.2, Preparation of hydrated salt / SiC composite phase change thermal storage material

[0208] (1) Add insulating and thermally conductive silicon carbide filler to the molten eutectic hydrated salt obtained in step 3.1. After mechanical stirring for 15 min, a eutectic hydrated salt / SiC mixture is obtained. The stirring speed is 60 r / min, and the silicon carbide particle size is 2-5 μm.

[0209] The mass fraction of silicon carbide is 80% of the mass of the eutectic hydrate salt.

[0210] (2) The eutectic hydrated salt / SiC mixture after being thoroughly and uniformly mixed is loaded into a crucible, and an appropriate amount of aluminum dihydrogen phosphate binder is added to obtain process mixture A.

[0211] The aluminum dihydrogen phosphate content is 4.5% of the mass of the eutectic hydrate salt / SiC mixture.

[0212] (3) Place the process mixture A obtained in step (2) into a crucible, put the crucible into a drying oven at 120°C and dry for 6 hours. Then close the drying oven and let it cool naturally to room temperature before taking it out to obtain process mixture B.

[0213] (4) Take out the cooled process mixture B and sinter it with a specific heating program to obtain process mixture C;

[0214] The heating process is as follows: heat from room temperature to 50°C for 40 minutes and hold for 20 minutes; heat to 75°C for 40 minutes and hold for 20 minutes; heat to 100°C for 30 minutes and hold for 30 minutes; and hold at the highest sintering temperature of 100°C for 1 hour.

[0215] (5) After the heat preservation process in step (4) is completed, take out the process mixture C in the crucible and put it into a planetary ball mill. Dry grind the mixture at a ball-to-material ratio of 1:1 and a speed of 100r / min until the particle size of the mixture is 10-20μm to obtain the hydrated salt / SiC composite phase change filler.

[0216] Step 3.3, Weigh the polyurethane base material

[0217] Specifically, the diisocyanate is 4,4'-dicyclohexylmethane diisocyanate, which accounts for 25% of the mass of the polyurethane base material;

[0218] Specifically, the polyether glycol is polypropylene glycol, and its mass content is 15% of the polyurethane prepolymer;

[0219] Specifically, the chain extender is 1,5-pentanediol, and its mass content is 2.5% of the polyurethane prepolymer;

[0220] Specifically, the hydrophilic chain extender is 2,2-dimethylolpropionic acid, and its mass content is 2% of the polyurethane prepolymer;

[0221] Specifically, the catalyst is dibutyltin oxide, and its mass content is 3.5% of the polyurethane prepolymer;

[0222] Specifically, the neutralizing agent is triethanolamine, and its mass content is 2% of the polyurethane prepolymer.

[0223] Specifically, the solvent is N,N-dimethylformamide, and its mass content is 50% of that of the polyurethane prepolymer.

[0224] Step 3.4, Preparation of polyurethane prepolymer

[0225] (1) Weigh the diisocyanate, polyether glycol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent according to the set mass ratio;

[0226] (2) Dry the weighed polyether glycol at 110°C for 5 hours.

[0227] (3) Take out the dried polyether diol from step (2) and put it into a three-necked round bottom flask. Pour nitrogen into the flask and start stirring. The stirring speed is 350 r / min and the stirring time is 20 min.

[0228] (4) Add the weighed catalyst and diisocyanate to the flask in step (3), start stirring, the stirring speed is 350 r / min, the stirring temperature is 88℃, and the stirring time is 60 min.

[0229] (5) Add the weighed hydrophilic chain extender to the flask in step (4), turn on the stirrer, the stirring speed is 350 r / min, the stirring temperature is 80℃, and the stirring time is 3h.

[0230] (6) Cool the reaction product of step (5) to 50°C, add the weighed neutralizing agent to carry out the neutralization reaction for 40 minutes to obtain polyurethane prepolymer.

[0231] Step 3.5, Preparation of modified hydrated salt / SiC composite phase change filler micro powder

[0232] (1) Add the hydrated salt / SiC composite phase change filler and silane coupling agent KH550 to a three-necked flask in a ratio of 25:1, and add toluene as a solvent for the reaction environment.

[0233] (2) Place the three-necked flask in a constant temperature oil bath, heat it to 90°C, introduce nitrogen gas and maintain the nitrogen atmosphere, start stirring and react for 6 hours at a stirring speed of 150 r / min.

[0234] (3) After the reaction is complete, the mixed solution in step (2) is vacuum filtered.

[0235] (4) After vacuum filtration, pour the hydrated salt / SiC composite phase change filler powder into a beaker, add deionized water, and sonicate for 60 minutes. After sonication, filter again.

[0236] (5) Add N,N-dimethylformamide to the hydrated salt / SiC composite phase change filler powder after filtration in step (4) and wash it twice.

[0237] (6) Place the cleaned hydrated salt / SiC composite phase change filler powder from step (5) into a vacuum drying oven; the drying oven needs to be preheated to 105℃ and kept at a constant temperature for 12 hours. The modified hydrated salt / SiC composite phase change filler powder is obtained.

[0238] Step 3.6: Prepare an insulating, high thermal conductivity, and anti-icing coating.

[0239] (1) Cool the reaction product of step 3.5 to 35°C and add it to the polyurethane prepolymer at 40% of the mass content of the polyurethane prepolymer to obtain a mixture.

[0240] (2) Add the weighed chain extender and solvent to the mixture obtained in the previous step, and start stirring. The stirring speed is 2000 r / min and the stirring temperature is 30 min. Finally, the insulating, high thermal conductivity and anti-icing coating is obtained.

[0241] Example 4

[0242] Step 1, prepare the adhesive coating;

[0243] The adhesive coating consists of component A, which includes epoxy resin E-44 and filler; and component B, which includes curing agent I, polyamide 650, DMP, and toughening agent.

[0244] Component A is obtained by mixing epoxy resin E-44, filler and modified nano boron nitride. Component B is obtained by mixing curing agent I, polyamide 650 and DMP. The adhesive coating is obtained by mixing and stirring components A, B and toughening agent. The amount of modified nano boron nitride is 3 wt% of the total mass of the adhesive coating.

[0245] Step 2, prepare the heat-insulating fiber;

[0246] (1) Silane, water, citric acid, urea and hexadecyltrimethylammonium chloride are mixed evenly, wherein the silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane and vinyltrimethoxysilane in a molar ratio of 3:5:2.4. After complete dissolution, the mixture is stirred vigorously for 1 hour to obtain organosilicon sol.

[0247] (2) The organosilicon sol was poured into a mold containing hollow glass fibers of the same size, allowing the fibers to be completely impregnated. The mixture was then aged by gel vibration at 80°C for 24 hours, followed by soaking in water at 60°C for 24 hours. Next, it was washed twice alternately with isopropanol and n-hexane solutions at 60°C, with an 8-hour interval between each wash. Finally, it was dried at room temperature and pressure for 72 hours to obtain flexible organosilicon aerogel composite fibers. The obtained flexible organosilicon aerogel composite material is a soft solid material, and its specific thickness and dimensions can be adjusted by changing the size of the mold.

[0248] Step 3, Prepare the heat storage protective film

[0249] Step 3.1, Preparation of hydrated salt phase change materials

[0250] Dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate were mixed in a beaker at a mass ratio of 176.67:13.86, and heated and stirred in a water bath at 55°C until they melted into a transparent liquid to obtain a eutectic hydrated salt.

[0251] Step 3.2, Preparation of hydrated salt / SiC composite phase change thermal storage material

[0252] (1) Add insulating and thermally conductive silicon carbide filler to the molten eutectic hydrated salt obtained in step 3.1. After mechanical stirring for 13 min, a eutectic hydrated salt / SiC mixture is obtained. The stirring speed is 100 r / min, and the silicon carbide particle size is 2-5 μm.

[0253] The mass fraction of silicon carbide is 70% of the mass of the eutectic hydrate salt.

[0254] (2) The eutectic hydrated salt / SiC mixture after being thoroughly and uniformly mixed is loaded into a crucible, and an appropriate amount of aluminum dihydrogen phosphate binder is added to obtain process mixture A.

[0255] The aluminum dihydrogen phosphate content is 3.5% of the mass of the eutectic hydrate salt / SiC mixture.

[0256] (3) Place the process mixture A obtained in step (2) into a crucible, put the crucible into a drying oven at 120°C and dry for 6 hours. Then close the drying oven and let it cool naturally to room temperature before taking it out to obtain process mixture B.

[0257] (4) Take out the cooled process mixture B and sinter it with a specific heating program to obtain process mixture C;

[0258] The heating process is as follows: heat from room temperature to 40°C for 40 minutes and hold for 20 minutes; heat to 70°C for 40 minutes and hold for 20 minutes; heat to 80°C for 30 minutes and hold for 30 minutes; and hold at the highest sintering temperature of 100°C for 1 hour.

[0259] (5) After the heat preservation process in step (4) is completed, take out the process mixture C in the crucible and put it into a planetary ball mill. Dry grind the mixture at a ball-to-material ratio of 1:1 and a speed of 100r / min until the particle size of the mixture is 10-20μm to obtain the hydrated salt / SiC composite phase change filler.

[0260] Step 3.3, Weigh the polyurethane prebase material

[0261] Specifically, the diisocyanate is isoflurone diisocyanate, and its mass content is 23% of the polyurethane base material;

[0262] Specifically, the polyether diol is polytetrahydrofuran diol, and its mass content is 17% of the polyurethane prepolymer;

[0263] Specifically, the chain extender is 1,5-pentanediol, and its mass content is 7.5% of the polyurethane prepolymer;

[0264] Specifically, the hydrophilic chain extender is 2,2-dimethylolpropionic acid, and its mass content is 1% of the polyurethane prepolymer;

[0265] Specifically, the catalyst is dibutyltin dilaurate, and its mass content is 1% of the polyurethane prepolymer;

[0266] Specifically, the neutralizing agent is tripropylamine, and its mass content is 0.5% of the polyurethane prepolymer.

[0267] Specifically, the solvent is N,N-dimethylformamide, and its mass content is 50% of that of the polyurethane prepolymer.

[0268] Step 3.4, Preparation of polyurethane prepolymer

[0269] (1) Weigh the diisocyanate, polyether glycol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent according to the set mass ratio;

[0270] (2) Dry the weighed polyether glycol at 110°C for 5 hours.

[0271] (3) Take out the dried polyether diol from step (2) and put it into a three-necked round bottom flask. Pour nitrogen into the flask and start stirring. The stirring speed is 350 r / min and the stirring time is 20 min.

[0272] (4) Add the weighed catalyst and diisocyanate to the flask in step (3), start stirring, the stirring speed is 350 r / min, the stirring temperature is 88℃, and the stirring time is 40 min.

[0273] (5) Add the weighed hydrophilic chain extender to the flask in step (4), turn on the stirrer, the stirring speed is 350 r / min, the stirring temperature is 80℃, and the stirring time is 3h.

[0274] (6) Cool the reaction product of step (5) to 50°C, add the weighed neutralizing agent to carry out the neutralization reaction for 30 minutes to obtain polyurethane prepolymer.

[0275] Step 3.5, Preparation of modified hydrated salt / SiC composite phase change filler micro powder

[0276] (1) Add the hydrated salt / SiC composite phase change filler and silane coupling agent KH550 to a three-necked flask in a ratio of 25:1, and add toluene as a solvent for the reaction environment.

[0277] (2) Place the three-necked flask in a constant temperature oil bath, heat it to 90°C, introduce nitrogen gas and maintain the nitrogen atmosphere, start stirring and react for 6 hours at a stirring speed of 110 r / min.

[0278] (3) After the reaction is complete, the mixed solution in step (2) is vacuum filtered.

[0279] (4) After vacuum filtration, pour the hydrated salt / SiC composite phase change filler powder into a beaker, add deionized water, and sonicate for 50 minutes. After sonication, filter again.

[0280] (5) Add N,N-dimethylformamide to the hydrated salt / SiC composite phase change filler powder after filtration in step (4) and wash it twice.

[0281] (6) Place the cleaned hydrated salt / SiC composite phase change filler powder from step (5) into a vacuum drying oven; the drying oven needs to be preheated to 105℃ and kept at a constant temperature for 12 hours. The modified hydrated salt / SiC composite phase change filler powder is obtained.

[0282] Step 3.6: Prepare an insulating, high thermal conductivity, and anti-icing coating.

[0283] (1) Cool the reaction product of step 3.5 to 35°C and add it to the polyurethane prepolymer at 40% of the mass content of the polyurethane prepolymer to obtain a mixture.

[0284] (2) Add the weighed chain extender and solvent to the mixture obtained in the previous step, and start stirring. The stirring conditions are 1500 r / min for 40 min, and finally the insulating, high thermal conductivity and anti-icing coating is obtained.

[0285] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades, characterized in that, The preparation process is as follows: an adhesive coating is applied to the blade substrate, then heat insulation fiber is laid, and then another layer of adhesive coating is applied. A heat storage protective film is placed on the adhesive coating. After the adhesive coating dries, an insulating, high-conductivity heat storage and anti-icing film is obtained. The heat-insulating fiber is a flexible organosilicon aerogel composite fiber; The flexible organosilicon aerogel composite fiber is composed of organosilicon sol and hollow glass fiber; The thermal storage protective film is composed of hydrated salt / SiC composite phase change filler and water-based polyaspartic acid ester resin crosslinked by an adhesive coating. The hydrated salt / SiC composite phase change filler is composed of eutectic hydrated salt and silicon carbide. The eutectic hydrated salt is composed of dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate. The adhesive coating is a polyurethane-modified epoxy resin adhesive with modified nano-boron nitride added, wherein the modified nano-boron nitride is boron nitride encapsulated in polydopamine.

2. The method for preparing a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades according to claim 1, characterized in that, The preparation method of the organosilicon aerogel composite fiber is as follows: (1) Mix silane, water, citric acid, urea and hexadecyltrimethylammonium chloride, stir and dissolve completely to obtain organosilicon sol; (2) Pour the silicone sol into a mold containing hollow glass fibers. The silicone sol completely impregnates the hollow glass fibers. After oscillation aging, the oscillated aged material is soaked in water. After being washed alternately with isopropanol and n-hexane, it is dried at room temperature and pressure to obtain flexible silicone aerogel composite fiber.

3. The method for preparing a lightning protection, heat storage, and anti-icing protective film suitable for the leading edge of wind turbine blades according to claim 2, characterized in that, The silane is a mixture of methyltrimethoxysilane, dimethyldimethoxysilane, and vinyltrimethoxysilane.

4. The method for preparing a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades according to claim 1, characterized in that, The preparation process of the adhesive coating is as follows: modified nano boron nitride is added during the preparation of component A of the polyurethane modified epoxy resin adhesive. After mixing components A and B of the polyurethane modified epoxy resin adhesive, the mixture is stirred evenly to obtain the adhesive coating.

5. The method for preparing a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades according to claim 4, characterized in that, The preparation process of the modified boron nitride nanoparticles is as follows: (1) Place the boron nitride raw material in water and stir at high speed to obtain a boron nitride suspension; (2) Add tris(hydroxymethyl)aminomethane to water to obtain tris(hydroxymethyl)aminomethane buffer. Mix tris(hydroxymethyl)aminomethane buffer and boron nitride suspension, add polydopamine, stir, add NaOH to adjust the pH of the system to 8.5, stir to obtain a mixed solution; (3) After centrifuging the mixed solution obtained in step (2) several times, collect the precipitate in the lower layer each time and freeze-dry it to obtain boron nitride encapsulated with polydopamine, which is modified nano boron nitride.

6. The method for preparing a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades according to claim 1, characterized in that, The preparation process of the heat storage protective film is as follows: Step 1: Mix the hydrated salt / SiC composite phase change filler and silane coupling agent KH550, then add toluene to obtain a mixed system; place the mixed system in a constant temperature oil bath vacuum filter pot, introduce nitrogen gas and stir. After the reaction is complete, perform vacuum filtration. After ultrasonic treatment, perform vacuum filtration again. Wash the filtered product with N,N-dimethylformamide and dry it to obtain the modified hydrated salt / SiC composite phase change filler micro powder. Step 2: Mix the hydrated salt / SiC composite phase change filler powder and polyurethane prepolymer, add chain extender and stir to obtain an insulating, high thermal conductivity and anti-icing dispersion. Step 3: Add dispersant, titanium dioxide, carbon black, anti-settling agent, defoamer, leveling agent, light stabilizer, ultraviolet absorber and solvent to the insulating high thermal conductivity anti-icing dispersion in sequence, stir evenly and disperse to obtain coating A; Step 3: Mix coating A and water-based isocyanate to obtain a heat storage coating; Step 4: Vacuum-fill the heat storage coating into the film-forming mold, and let it dry to obtain a heat storage protective film.

7. The method for preparing a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades according to claim 6, characterized in that, In step 1, the preparation process of the hydrated salt / SiC composite phase change filler is as follows: (1) Mix dipotassium hydrogen phosphate hexahydrate and disodium hydrogen phosphate dodecahydrate and heat and stir to obtain a molten eutectic hydrated salt; (2) Add insulating and thermally conductive filler silicon carbide to molten eutectic hydrated salt, and stir to obtain eutectic hydrated salt / SiC mixture; (3) Add aluminum dihydrogen phosphate binder to the eutectic hydrated salt / SiC mixture to obtain a mixture; (4) The mixture is dried and then sintered to obtain the sintered product; (5) The sintered product was ball-milled to obtain a hydrated salt / SiC composite phase change filler.

8. The method for preparing a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades according to claim 6, characterized in that, In step 2, the preparation process of the polyurethane prepolymer is as follows: Dry polyether glycol is placed in a container, nitrogen gas is introduced into the container, and after stirring, the first catalyst and diisocyanate are added. After stirring, a hydrophilic chain extender is added, and the reaction is carried out. After the reaction product is cooled, a neutralizing agent is added to carry out a neutralization reaction to obtain polyurethane prepolymer.

9. A method for preparing a lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades according to claim 8, characterized in that, The hydrophilic chain extender is 2,2-dimethylolpropionic acid, dimethylolbutyric acid, or a mixture thereof; The first catalyst is one or more of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide.

10. A lightning protection, heat storage, and anti-icing protective film for the leading edge of wind turbine blades, prepared by any one of claims 1-9, characterized in that, include: Thermal insulation fibers are installed on the outside of the wind turbine blades; A heat storage protective film is placed outside the heat insulation fiber; The heat insulation fiber and the wind turbine blade are bonded together by an adhesive coating, and the heat storage protective film and the heat insulation fiber are bonded together by an adhesive coating.

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