An anti-icing heat storage film suitable for wind turbine blades and its preparation method

Abstract

The present invention discloses an anti-icing heat storage film suitable for wind turbine blades and a preparation method thereof, belonging to the technical field of wind turbine blade coatings, comprising a hollow glass fiber cloth arranged on the outside of the wind turbine blade, with a heat storage protective film arranged outside the hollow glass fiber cloth; the wind turbine blade and the hollow glass fiber cloth are bonded by an adhesive coating, and the hollow glass fiber cloth and the heat storage protective film are bonded by an adhesive coating. The heat storage film utilizes the cavity in its unique spherical hollow structure to form an insulation layer to prevent heat conduction; in order to ensure that the thickness of the heat storage protective layer is consistent after construction on the blade surface, the material is prefabricated into a heat storage protective film before construction, and the thickness of the film can be adjusted according to the actual situation of the on-site application. The phase change heat storage material in the heat storage film selects hydrated salt as the phase change component, which has the advantages of high phase change enthalpy, high energy storage density, large thermal conductivity and low price.

Description

Technical Field

[0001] The present invention belongs to the technical field of wind turbine blade coatings, and in particular relates to an anti-icing heat storage film suitable for wind turbine blades and a preparation method thereof. Background Art

[0002] Wind power, a clean, renewable energy source, has experienced rapid development in recent years, with installed capacity increasing exponentially. As the sole core component for capturing wind energy, the stable and safe operation of blades directly impacts the power generation of wind turbines.

[0003] Some wind turbines are located in high mountains or border areas prone to freezing, where the temperature swings between day and night are significant. These areas experience abundant sunlight and relatively high temperatures during the day, but temperatures drop below freezing at night, making ice formation very likely to form on the blades. Once ice forms on the blades, it can lead to mass imbalance and asymmetric loads, which in turn can reduce turbine output, causing mechanical failures or even downtime. Furthermore, during blade operation, when the ice loses its adhesion, it can easily break off. Under the influence of gravity and centrifugal force, the ice fragments can be thrown far away, potentially damaging personnel and equipment around the turbine.

[0004] Currently available wind turbine blade anti-icing / de-icing technologies mainly include active de-icing and passive de-icing. Active de-icing methods include electric heating de-icing and gas heating de-icing, while passive de-icing methods include super-hydrophobic de-icing. The advantage of active de-icing technology is that it can directly and effectively melt the ice, but there are the following problems: (1) Blade gas heating de-icing technology is suitable for situations where ice is not serious. This is because the low heat transfer efficiency of fiberglass leads to unsatisfactory de-icing effect, and it also consumes a lot of power. (2) Blade electric heating de-icing has been proven to be the most effective and direct de-icing technology. However, considering the risk of lightning strikes, electric heating films can only be laid in local areas. In addition, the cost of active de-icing technology is relatively high. Passive super-hydrophobic de-icing is a technology that inhibits ice formation from the source. It is low-cost and can inhibit ice formation on the surface of wind turbine blades in low-temperature and high-humidity environments. However, the super-hydrophobic coating applied to wind turbine blades has a low surface energy that seriously affects adhesion, poor reliability and durability, and its hydrophobicity is easily reduced. The effective de-icing period is generally only 3 to 6 months. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide an anti-icing heat storage film suitable for wind turbine blades and a preparation method thereof, so as to solve the technical problems in the prior art of poor reliability and durability of superhydrophobic coatings and a short effective anti-icing period.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] An anti-icing heat storage film suitable for wind turbine blades, comprising a hollow glass fiber cloth arranged on the outside of the wind turbine blade, with a heat storage protective film arranged outside the hollow glass fiber cloth; the wind turbine blade and the hollow glass fiber cloth are bonded by an adhesive coating, and the hollow glass fiber cloth and the heat storage protective film are bonded by an adhesive coating; the thickness of the heat storage protective film is 200 μm to 500 μm;

[0008] The bonding coating is a polyurethane-modified epoxy resin, and hollow microspheres are added to the polyurethane-modified epoxy resin;

[0009] The heat storage protective film comprises a water-based polyaspartic acid ester polyurea base resin, a binder, heat storage microcapsules and additives; the binder is a PTFE water-based emulsion; the heat storage microcapsules are dispersed in the water-based polyaspartic acid ester polyurea base resin;

[0010] The heat storage microcapsule is composed of expanded graphene and a hydrated salt phase change material, the hydrated salt phase change material is filled in the pores of the expanded graphene, and the hydrated salt phase change material is composed of dipotassium hydrogen phosphate hexahydrate, glycine and disodium hydrogen phosphate dodecahydrate;

[0011] The water-based polyaspartic acid ester polyurea base resin consists of a heat-storage polyaspartic acid ester dispersion and water-based isocyanate. The heat-storage polyaspartic acid ester dispersion consists of polyetheramine, polyaspartic acid ester and diisocyanate.

[0012] A further improvement of the present invention is:

[0013] Preferably, the added amount of the hollow microspheres is 4.5% to 6.0 wt% of the mass of the polyurethane-modified epoxy resin.

[0014] Preferably, the particle size distribution of the hollow microspheres added to the polyurethane-modified epoxy resin is as follows: 270-325 mesh accounts for 20%, 500-600 mesh accounts for 60%, and 800-1250 mesh accounts for 20%, based on mass fraction.

[0015] Preferably, in terms of mass fraction, the water-based polyaspartic acid ester polyurea base resin in the heat storage protective film accounts for 40% to 50%, the binder accounts for 20% to 30%, and the heat storage microcapsules account for 20% to 40%.

[0016] Preferably, the additives include dispersants, titanium dioxide, carbon black, anti-settling agents, defoaming agents, leveling agents, light stabilizers and solvents.

[0017] A method for preparing an anti-icing heat storage film suitable for a wind turbine blade comprises the following steps: coating an adhesive on a polished wind turbine blade substrate, placing a hollow glass fiber cloth on the adhesive, coating the hollow glass fiber cloth with an adhesive, and placing a heat storage protective film on the adhesive;

[0018] The preparation method of the heat storage protective film comprises the following steps:

[0019] Step 1: adding a hydrated salt phase change material to expanded graphene and stirring to obtain a heat storage microcapsule suspension;

[0020] Step 2, adding PTFE emulsion dropwise to the mixture of polyetheramine and polyaspartic acid ester, stirring evenly after the addition, to obtain process mixture 1;

[0021] Step 3, adding the heat storage microcapsule suspension to the process mixture 1 dropwise, stirring evenly to obtain the process mixture 2;

[0022] Step 4, adding diisocyanate dropwise to the process mixture 2 to obtain the process mixture 3;

[0023] Step 5, adding water dropwise to the mixture of process 3 and stirring evenly to obtain component A;

[0024] Step 6, adding additives to component A;

[0025] Step 7, adding aqueous isocyanate dropwise to component A with the additive, and stirring evenly to obtain a heat storage coating;

[0026] Step 8: Vacuum-infuse the heat storage coating into a film-making mold, and form a film after solidification to obtain a heat storage protective film.

[0027] Preferably, in step 1, the preparation process of the hydrated salt phase change material is to mix hydrated dipotassium hydrogen phosphate, glycine and disodium hydrogen phosphate dodecahydrate in a mass ratio of 176.67:13.86:0.99, place it in a 55°C water bath, heat and stir until it melts into a transparent liquid, and obtain the hydrated salt phase change material.

[0028] Preferably, in step 2, the polyaspartic acid ester is a mixture of polyaspartic acid ester F420 and polyaspartic acid ester F520 in a molar ratio of (4-5):1.

[0029] Preferably, in step 2, the mass ratio of the polyaspartic acid ester to the polyetheramine is (3-8):1.

[0030] Preferably, the molar ratio of the diisocyanate added in step 4 to the polyetheramine in step 2 is (1-1.3):1;

[0031] In step 7, the molar ratio of -NH in component A to -NCO in the aqueous isocyanate is 1:1.2.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention discloses an anti-icing heat storage film suitable for wind turbine blades. The film utilizes a protective film adhesive method, with insulating hollow fibers as the fibers. Hollow microspheres are added to the adhesive epoxy resin coating, utilizing the numerous cavities within the unique spherical hollow structure to form an insulating layer to prevent heat conduction. To ensure a consistent thickness of the heat storage protective layer after construction on the blade surface, the material is prefabricated into a heat storage protective film before construction, and the film thickness can be adjusted based on the actual on-site application. The adhesive utilizes a polyurethane-modified epoxy resin coating, which effectively connects the substrate and the heat storage protective film, enhancing the bonding strength. The phase change heat storage material in the heat storage film uses hydrated salt as the phase change component. This material has the advantages of high phase change enthalpy, high energy storage density, high thermal conductivity, and low price. It can improve the heat storage performance of the heat storage coating and more effectively absorb and store daytime solar heat within the coating, preventing ice formation and damage to the wind turbine blades when the temperature drops at night. At the same time, the material selection should take into account its impact on blade performance and weight to ensure it does not affect blade performance and weight, thereby improving wind turbine efficiency. Expanded graphite is used as a thermal conductor and support material. Its loose structure, large specific surface area, and strong adsorption capacity allow the phase change component to be evenly adsorbed within the pores of the expanded graphite due to its capillary and surface tension properties. The two phases are tightly bonded at the interface, preventing leakage during the phase change process. Its melting or decomposition temperature must be higher than the phase change temperature of the phase change component to ensure shape stability and processability, ensuring the coating's adhesion and reliability, enabling it to maintain good heat absorption and release even in harsh environments. The addition of a nucleating agent and stirring methods address overcooling. The addition of a separation inhibitor ensures composition stability and reduces phase separation. An optimized formulation reduces the manufacturing cost of the thermal storage coating. This thermal storage film utilizes lower-cost raw materials, simplifies the production process, and improves production efficiency. Furthermore, by improving the safety and reliability of wind turbines, it can indirectly enhance the economic benefits of wind power generation. This thermal storage film also offers the following advantages:

[0034] 1. The thermal storage coating of the present invention possesses excellent heat absorption and storage properties, effectively absorbing and storing sunlight and heat within the coating. This prevents blade burns from strong daylight and, when temperatures drop at night, prevents icing on wind turbine blades, thereby more effectively protecting the blades from damage and improving the safety of wind turbines. 2. The thermal storage coating of the present invention is uniform and stable, making it less susceptible to overcooling and phase separation issues. It does not increase blade weight, thereby impacting wind turbine efficiency. The thermal storage coating of the present invention is lighter and more suitable for wind turbine blades. 3. The thermal storage coating of the present invention has a simple preparation process and low heat storage costs. In areas with large daytime and nighttime temperature differences, it can reduce the cost of blade anti-icing and UV protection, thereby improving the economic benefits of wind power generation. Compared to existing technologies, the thermal storage coating of the present invention offers greater economic value. 4. The thermal storage coating of the present invention also provides additional protective features, such as UV protection and corrosion protection, further extending the service life and performance of blades. 5. The film ensures uniform thickness, which, compared to brush-on coatings, reduces the difficulty and time required for application. 6. Compared with other membranes, the adhesive uses polyurethane-modified epoxy resin coating, which greatly enhances the bonding strength and will not fall off after a period of use. 7. In order to ensure the uniform thickness of the heat storage protective layer on the blade surface after construction, the material is prefabricated into a heat storage protective film before construction. This can reduce the construction difficulty and shorten the construction period while ensuring construction quality. DETAILED DESCRIPTION

[0035] Figure 1 It is a structural schematic diagram of the present invention. DETAILED DESCRIPTION

[0037] The present invention is described in further detail below with reference to the accompanying drawings:

[0038] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0039] In this document, unless otherwise specified, “include,” “including,” “contains,” “has” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0040] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0041] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0042] In the description of the present invention, it should be noted that the terms "center", "up", "down", "left", "right", "vertical", "horizontal", "inside", "outside" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention; the terms "first", "second", and "third" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance; in addition, unless otherwise expressly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be a communication between the internal parts of two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0043] The first aspect of the present invention discloses a heat storage film for a wind turbine blade. The heat storage film is arranged on the wind turbine blade and includes an adhesive coating, a hollow glass fiber cloth, an adhesive coating and a heat storage protective film arranged in sequence from the inside to the outside.

[0044] Specifically, the bonding coating is an epoxy resin coating, which is used to bond the surface of wind turbine blades and hollow glass fiber cloth, as well as to bond hollow glass fiber cloth and heat storage protective film. The polyurethane-modified epoxy resin is a material obtained by modifying epoxy resin using a polyurethane molecular structure. The coating is a commercially available coating, and it can also be a separately prepared coating. During the preparation process, the epoxy resin and polyurethane prepolymer are usually preheated and vacuum-treated to eliminate bubbles. Subsequently, the two are mixed at a certain temperature and a catalyst is added for high-speed stirring to finally obtain the modified epoxy resin. Exemplary, the polyurethane-modified epoxy resin composition can be epoxy resin E-44, blocked polyurethane prepolymer toughening agent A, accelerator DMP-30, curing agent 1, polyamide 650, TDI (toluene diisocyanate) and quartz sand. This material introduces polyurethane elastic molecules into epoxy resin. It was found that 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 serve as a bridge between the epoxy resin substrate and the polyurethane system heat storage protective film.

[0045] The epoxy resin coating of the present invention is added with hollow microspheres, the main components of which are silicon dioxide (SiO2) and aluminum oxide (Al2O3). The spherical hollow microspheres have a hollow cavity inside. The viscosity of the epoxy resin coating increases with the addition of microspheres. Too high a viscosity will affect the construction of the coating, so the addition amount of microspheres is more appropriately between 4.5% and 6.0wt%. The gradation of microspheres has a certain influence on the thermal insulation effect and coating performance of the coating system. Large particle size of microspheres has a good thermal insulation effect of the coating, but the coating surface is rough and has many gaps, and the coating has poor stain resistance. Small particle size of microspheres has a smooth and flat coating surface, and the coating has good stain resistance, but the coating has a slightly poor reflective heat insulation effect. Therefore, the particle size needs to be matched so that the coating has a good heat insulation effect of reflecting solar heat and a smooth and flat coating surface, and the coating has good stain resistance. Through experiments, it was determined that when the particle size distribution of microbeads is 270-325 mesh accounting for 20%, 500-600 mesh accounting for 60%, and 800-1250 mesh accounting for 20%, the overall effect is better.

[0046] The thickness of the hollow glass fiber cloth is 0.08-0.25 mm, and the main structure of the hollow glass fiber cloth is glass fiber, the interior of the glass fiber is hollow.

[0047] The thermal storage protective film comprises a water-based polyaspartic acid ester polyurea base resin, a binder, thermal storage microcapsules, and additives, with the mass fractions of the three being 40% to 50%, 20% to 30%, and 20% to 40%, respectively. The binder is a PTFE aqueous emulsion with a solids content of 90%. The thermal storage microcapsules are composed of expanded graphite and a hydrated salt phase change material, which is adsorbed within the pores of the expanded graphite. The hydrated salt phase change material is composed of dipotassium hydrogen phosphate hexahydrate, disodium hydrogen phosphate dodecahydrate, and glycine.

[0048] In the above-disclosed heat storage protective film, the water-based polyaspartic acid ester polyurea base resin serves as the base material of the wind turbine blade coating. The binder can evenly bond and fix the inorganic phase change filler in the base material of the coating, thereby improving the dispersibility of the entire phase change filler. The phase change filler is composed of expanded graphite and hydrated salt phase change material. The expanded graphite has a loose and porous worm-like structure, and the hydrated salt phase change material is used to store external heat or release heat according to changes in its own morphology.

[0049] The thermal storage microcapsules use dipotassium hydrogen phosphate hexahydrate as the phase change matrix, disodium hydrogen phosphate dodecahydrate as a nucleating agent to facilitate nucleation of the dipotassium hydrogen phosphate hexahydrate in expanded graphite, glycine as a phase change separation inhibitor, and expanded graphite as a thermal conductor and support material. The water-based polyaspartic acid ester polyurea base resin is used as the base material. A eutectic hydrate salt is prepared from dipotassium hydrogen phosphate hexahydrate, disodium hydrogen phosphate dodecahydrate, and glycine. This eutectic hydrate salt is adsorbed into the expanded graphite to form a phase change filler. This phase change filler is then cross-linked with the water-based polyaspartic acid ester polyurea base resin via a binder to form the thermal storage coating.

[0050] In these substances, binary or multicomponent systems can exist in stable or metastable equilibrium with two distinct phases within a certain temperature and composition range, i.e., they exhibit immiscibility. Glycine prevents this phenomenon, ensuring that the multicomponent system remains in the same stable phase and has a uniform texture.

[0051] The water-based polyaspartic acid ester polyurea base resin consists of a heat-storage polyaspartic acid ester dispersion and water-based isocyanate, and the heat-storage polyaspartic acid ester dispersion consists of polyetheramine, polyaspartic acid ester and diisocyanate.

[0052] Specifically, the diisocyanate is a mixture of any one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0053] Specifically, the polyetheramine is a mixture of any one or more of polyetheramine M230, polyetheramine M1000 or polyetheramine 2000.

[0054] Specifically, the polyaspartic acid ester is a mixture of F420 and F520, and the molar ratio of polyaspartic acid ester F420 to polyaspartic acid ester F520 is (4-5):1.

[0055] Specifically, the molar ratio of polyetheramine to diisocyanate is 1:(1-1.3).

[0056] Specifically, the mass ratio of polyaspartic acid ester to polyetheramine is (3-8):1.

[0057] The molar ratio of -NH in the heat storage polyaspartic acid ester dispersion and -NCO in the aqueous isocyanate is 1:1.2.

[0058] Because the above-mentioned coating contains hydrated salt as a phase change material, it has excellent heat absorption and heat storage performance. It can effectively absorb light and heat and store it in the coating, avoiding strong light burning the blades during the day. At the same time, after the temperature drops at night, it can prevent the wind turbine blades from freezing, thereby more effectively protecting the blades from damage and improving the safety of the wind turbine. The heat storage coating has a uniform and stable state, is not prone to problems such as overcooling and phase separation immiscibility, does not increase the weight of the blades, and thus does not affect the efficiency of the wind turbine. At the same time, due to the particularity of the material selection, the heat storage coating is lighter and more suitable for the blades of wind turbines. The preparation process of the heat storage coating is simple, and the heat storage cost is low. For areas with large temperature differences between day and night, it can reduce the cost of blade anti-icing and anti-ultraviolet, which is beneficial to improving the economic benefits of wind power generation. The heat storage coating of the present invention can also provide additional protection functions, such as anti-ultraviolet, anti-corrosion, etc., which can further improve the service life and performance of the blades.

[0059] The second aspect of the present invention discloses a method for preparing a heat storage membrane, which uses dipotassium hydrogen phosphate hexahydrate as a phase change matrix, disodium hydrogen phosphate dodecahydrate as a nucleating agent, glycine as a phase change inhibitor, and expanded graphite as a thermal conductor and support material, wherein a water-based polyaspartic acid ester polyurea base resin is used. A eutectic hydrate salt is prepared from dipotassium hydrogen phosphate hexahydrate, disodium hydrogen phosphate dodecahydrate, and glycine. This eutectic hydrate salt is adsorbed in the expanded graphite to form a phase change filler. This phase change filler is cross-linked and mixed with the water-based polyaspartic acid ester polyurea base resin via a binder to form a heat storage membrane. The preparation method comprises the following steps:

[0060] Step 1: preparing expanded graphite;

[0061] Weigh an appropriate amount of expanded graphite raw material, place it in a microwave oven, and microwave heat it at 800W for 2-3 minutes. Place the expanded graphite in a vacuum oven at 100-120°C (vacuum degree -0.07-0.1MPa) for 2 hours. After drying, the expanded graphite is obtained.

[0062] The expanded graphite raw material is EG600, EG700 or EG800; the size of the expanded graphite raw material is ≤13um.

[0063] Step 2: Preparation of hydrated salt phase change material

[0064] Dipotassium hydrogen phosphate hexahydrate, glycine, and disodium hydrogen phosphate dodecahydrate were mixed in a beaker at a mass ratio of 176.67:13.86:0.99, and the mixture was heated and stirred in a water bath at 55° C. until the mixture melted into a transparent liquid to obtain a hydrated salt phase change material.

[0065] Step 3: Preparation of heat storage microcapsules

[0066] The expanded graphite prepared in step 1 is added to the molten eutectic hydrated salt in step 2. After mechanical stirring and mixing for 10 to 15 minutes, the hydrated salt will penetrate into the pores of the expanded graphite to obtain a eutectic hydrated salt / graphite mixture as a microcapsule suspension.

[0067] The mass fraction of the expanded graphite is 5% to 15%.

[0068] Step 4: Preparation of heat storage protective film

[0069] The heat storage coating includes a water-based polyaspartic acid ester polyurea base material (the sum of the masses of polyetheramine, polyaspartic acid ester and diisocyanate), a binder, a phase change filler, and additives, with the mass content of each component being 40% to 50%, 20% to 30%, and 20% to 40% respectively.

[0070] (1) Weigh polyetheramine and polyaspartic acid ester according to the above ratio respectively, and place them in a four-necked flask for vacuum drying; the vacuum drying conditions are: 100-105°C, -0.07-0.04 MPa, and time is 1-1.5 h.

[0071] (2) Weigh the diisocyanate according to the above ratio and place it in a constant pressure titration funnel.

[0072] (3) The binder and phase change filler are weighed in the above proportions, with the mass contents of the two in the coating being 20% ​​to 30% and 20% to 40% respectively, and are placed in a constant pressure funnel respectively.

[0073] (4) The four-necked flask containing the polyetheramine and polyaspartic acid ester in step (1) was taken out from the vacuum drying oven, nitrogen was introduced into the flask while the stirrer was turned on, and the temperature was lowered to 30-50°C.

[0074] (5) Open the constant pressure funnel containing the binder PTFE emulsion in step (3), and drop the binder into the four-necked flask in step (4). The addition time is 1 to 2 hours, and stirring is turned on at 40 to 70 r / min. After the addition is completed, stirring is stopped to obtain process mixture 1.

[0075] (6) Open the constant pressure funnel containing the phase change filler in step (3), and add the phase change filler dropwise into the four-necked flask in step (5). The addition time is 1 to 2 hours, and stirring is started at 50 to 60 r / min. After the addition is completed, stirring is stopped to obtain process mixture 2.

[0076] (7) Open the constant pressure titration funnel in step (2) and add diisocyanate dropwise to the four-necked flask at a constant speed for 1 to 1.5 hours to obtain process mixture three.

[0077] (8) After the dripping is completed, rinse the constant pressure titration funnel with a certain amount of dipropylene glycol dimethyl ether and drip it into the four-necked flask, raise the temperature to 50-70°C, and react at this constant temperature for 2-3 hours.

[0078] (9) Replace the constant pressure titration funnel and slowly add deionized water to the reaction product of step (8) while stirring. Too fast a dropping speed can easily lead to uneven dispersion and agglomeration. The dropping time is 0.5 to 1 h, the stirring speed is 1000 to 1300 r / min, and the stirring time is 0.3 to 0.5 h to obtain component A.

[0079] (10) Dispersant (accounting for 1% to 1.5% of the total mass fraction of component A, acrylic dispersant), titanium dioxide (accounting for 25% to 30% of the mass of component A, filler for coloring), carbon black (accounting for 0.05% to 0.1% of the mass of component A, for coloring and enhancing light absorption), anti-settling agent (accounting for 0.5% to 1% of the mass of component A, nano-silicon dioxide or polyamide wax), defoaming agent (accounting for 0.5% to 1% of the mass of component A, polydimethylsiloxane, fluorosilicone, ethylene glycol siloxane), leveling agent (accounting for 0.8% to 1% of the mass of component A, polyether polyester modified organic siloxane), light stabilizer (accounting for 0.05% to 0.1% of the mass of component A), and the like are added to the obtained component A in sequence. 0.5% to 1%, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), an ultraviolet absorber (accounting for 0.8% to 1.2% of the mass of the additive, a hydroxyphenylbenzotriazole ultraviolet absorber), and a solvent (propylene glycol methyl ether acetate, dimethyl sulfoxide, and xylene, accounting for 3% to 10% of the mass of component A) are added in sequence under low-speed stirring and mixed evenly, and then dispersed at a high speed of 2500 rpm / min, maintaining the temperature at 40°C for not less than 30 minutes, and the detected fineness is not higher than 50 μm to form an additive.

[0080] (11) According to the modified component A of the reaction product in step (9), the weight of the aqueous isocyanate was weighed, and the ratio of the two was calculated as n(—NCO):n(—NH)=1.2:1. Before trial use, the mixture obtained in step 10 and the aqueous isocyanate were fully stirred and mixed evenly to finally obtain the heat storage coating.

[0081] (12) The coating is vacuum-infused into a film-making mold. The bottom material of the mold is a polytetrafluoroethylene substrate, which is non-adhesive. The thickness of the infusion is controlled to be 200 μm to 500 μm. After being placed at room temperature for 24 hours, the finished heat storage protective film can be torn off and taken out. The environment during solidification can be vacuum or atmospheric.

[0082] In step 4, adhesive coating is first applied to the polished blade substrate, followed by laying hollow glass fiber cloth. Another layer of coating is then applied, and finally, the thermal storage protective film is bonded on top. The time between each application of adhesive coating and laying the glass fiber or thermal storage protective film is less than one hour. The adhesive coating has a thickness of 30-70 μm. After application, it partially penetrates the hollow glass fiber, connecting the hollow glass fiber cloth to the wind turbine blade surface, or connecting the hollow glass fiber cloth to the thermal storage protective film.

[0083] The following is further described with reference to specific embodiments:

[0084] Example 1

[0085] Step 1: preparing expanded graphite;

[0086] Weigh an appropriate amount of EG700 as the expanded graphite raw material and place it in a microwave oven at 800W for 2.5 minutes. Place the expanded graphite in a vacuum oven at 105°C (vacuum degree -0.07 to 0.1MPa) for 2 hours to obtain expanded graphite.

[0087] Step 2: Preparation of hydrated salt phase change material

[0088] 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, and the mixture was heated and stirred in a water bath at 55° C. until the mixture melted into a transparent liquid to obtain a hydrated salt phase change material.

[0089] Step 3: Preparation of heat storage microcapsules

[0090] The expanded graphite prepared in step 1 is added to the molten eutectic hydrated salt in step 2, wherein the mass fraction of the eutectic hydrated salt is 90% and the mass fraction of the expanded graphite is 10%. The two are mechanically stirred and mixed for 15 minutes to obtain a eutectic hydrated salt / graphite mixture.

[0091] Step 4: Preparation of heat storage coating

[0092] The mass proportion of the water-based polyaspartic acid ester polyurea base material is set to 45%, the mass proportion of the binder is set to 25%, and the mass proportion of the phase change filler is set to 35%.

[0093] (1) Polyetheramine and polyaspartic acid ester were weighed in a molar ratio of 1:5 and placed in a four-necked flask for vacuum drying; the vacuum drying conditions were: 102°C, -0.06 MPa, and time: 1.5 h. In this embodiment, the polyetheramine was polyetheramine M230, and the molar ratio of polyaspartic acid ester F420 to polyaspartic acid ester F520 in the polyaspartic acid ester was 4.5:1.

[0094] (2) Weigh diisocyanate at a molar ratio of polyetheramine to diisocyanate of 1:1.2 and place it in a constant pressure titration funnel. In this embodiment, the diisocyanate is isophorone diisocyanate.

[0095] (3) The mass contents of the binder and phase change filler in the coating are 25% and 35% respectively, and they are placed in a constant pressure funnel respectively.

[0096] (4) The four-necked flask containing polyetheramine and polyaspartic acid ester in step (1) was taken out from a vacuum drying oven, nitrogen was introduced into the flask while the stirrer was turned on, and the temperature was lowered to 40°C.

[0097] (5) Open the constant pressure funnel containing the binder PTFE emulsion in step (3) and drop the binder into the four-necked flask in step (4). The addition time is 1.5 hours, and stirring is turned on at 50 r / min. After the addition is completed, stirring is stopped.

[0098] (6) Open the constant pressure funnel with the phase change filler in step (3), and add the phase change filler dropwise to the four-necked flask in step (5). The addition time is 1.5 hours, and stirring is turned on at 55 r / min. After the addition is completed, stirring is stopped.

[0099] (7) Open the constant pressure titration funnel in step (2) and add diisocyanate dropwise to the four-necked flask at a constant rate over 1.2 hours. The molar ratio of polyetheramine to diisocyanate is 1:1.2.

[0100] (8) After the dripping is completed, a certain amount of dipropylene glycol dimethyl ether is used to rinse the constant pressure titration funnel and drip into the four-necked flask, and the temperature is raised to 60°C and the reaction is kept at this temperature for 2.5 hours.

[0101] (9) Replace the constant pressure titration funnel and slowly add deionized water to the reaction product of step (8) dropwise for 0.8 h, with a stirring speed of 1200 r / min and a stirring time of 0.4 h to obtain component A.

[0102] (10) Acrylic dispersant was added to the heat storage polyaspartic acid ester dispersion in sequence, accounting for 1.2% of the total mass fraction of component A; titanium dioxide, accounting for 28% of the mass of component A; carbon black, accounting for 0.08% of the mass of component A; anti-settling agent was nano-silica, accounting for 0.8% of the mass of component A; defoaming agent, accounting for 0.8% of the mass of component A; leveling agent, accounting for 0.9% of the mass of component A; light stabilizer, which was bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8-(1,2,2,6, A mixture of 6-pentamethyl-4-piperidinyl) sebacate, accounting for 0.7% of the mass of component A; a UV absorber, a hydroxyphenylbenzotriazole UV absorber, accounting for 1% of the mass of component A; and a solvent, a mixture of propylene glycol methyl ether acetate, dimethyl sulfoxide, and xylene, accounting for 6% of the mass of component A. The components are added sequentially under low-speed stirring and mixed until uniformly mixed, and then dispersed at a high speed of 2500 rpm / min, maintaining the temperature at 40°C for not less than 30 minutes, and the fineness detected is not higher than 50 μm to obtain component A with added additives;

[0103] (10) According to the weight of component A in step (9), the weight of the aqueous isocyanate is weighed, and the molar ratio of -NCO in the aqueous isocyanate and the molar ratio of -NH in component A are calculated as 1.2:1, and the two are fully stirred and mixed to obtain a heat storage coating.

[0104] Example 2

[0105] Step 1: preparing expanded graphite;

[0106] Weigh an appropriate amount of EG600 as the expanded graphite raw material and place it in a microwave oven at 800W for 2 minutes. Place the expanded graphite in a vacuum oven at 110°C (vacuum degree -0.07 to 0.1MPa) for 2 hours to obtain expanded graphite.

[0107] Step 2: Preparation of hydrated salt phase change material

[0108] 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, and the mixture was heated and stirred in a water bath at 55° C. until the mixture melted into a transparent liquid to obtain a hydrated salt phase change material.

[0109] Step 3: Preparation of heat storage microcapsules

[0110] The expanded graphite prepared in step 1 is added to the molten eutectic hydrated salt in step 2, wherein the mass fraction of the eutectic hydrated salt is 85% and the mass fraction of the expanded graphite is 15%. The two are mechanically stirred and mixed for 12 minutes to obtain a eutectic hydrated salt / graphite mixture.

[0111] Step 4: Preparation of heat storage coating

[0112] The mass proportion of the water-based polyaspartic acid ester polyurea base material is set to 50%, the mass proportion of the binder is set to 30%, and the mass proportion of the phase change filler is set to 20%.

[0113] (1) Polyetheramine and polyaspartic acid ester were weighed in a molar ratio of 1:5 and placed in a four-necked flask for vacuum drying; the vacuum drying conditions were: 102°C, -0.06 MPa, and time: 1.5 h. In this embodiment, the polyetheramine was polyetheramine M230, and the molar ratio of polyaspartic acid ester F420 to polyaspartic acid ester F520 in the polyaspartic acid ester was 4.5:1.

[0114] (2) Weigh diisocyanate at a molar ratio of polyetheramine to diisocyanate of 1:1.2 and place it in a constant pressure titration funnel. In this embodiment, the diisocyanate is isophorone diisocyanate.

[0115] (3) The mass contents of the binder and phase change filler in the coating are 25% and 35% respectively, and they are placed in a constant pressure funnel respectively.

[0116] (4) The four-necked flask containing polyetheramine and polyaspartic acid ester in step (1) was taken out from a vacuum drying oven, nitrogen was introduced into the flask while the stirrer was turned on, and the temperature was lowered to 40°C.

[0117] (5) Open the constant pressure funnel containing the binder PTFE emulsion in step (3) and drop the binder into the four-necked flask in step (4). The addition time is 1.5 hours, and stirring is turned on at 50 r / min. After the addition is completed, stirring is stopped.

[0118] (6) Open the constant pressure funnel with the phase change filler in step (3), and add the phase change filler dropwise to the four-necked flask in step (5). The addition time is 1.5 hours, and stirring is turned on at 55 r / min. After the addition is completed, stirring is stopped.

[0119] (7) Open the constant pressure titration funnel in step (2) and add diisocyanate dropwise to the four-necked flask at a constant rate over 1.2 hours. The molar ratio of polyetheramine to diisocyanate is 1:1.2.

[0120] (8) After the dripping is completed, a certain amount of dipropylene glycol dimethyl ether is used to rinse the constant pressure titration funnel and drip into the four-necked flask, and the temperature is raised to 60°C and the reaction is kept at this temperature for 2.5 hours.

[0121] (9) Replace the constant pressure titration funnel and slowly add deionized water to the reaction product of step (8) dropwise for 0.8 h, with a stirring speed of 1200 r / min and a stirring time of 0.4 h to obtain component A.

[0122] (10) Acrylic dispersant was added to the heat storage polyaspartic acid ester dispersion in sequence, accounting for 1% of the total mass fraction of component A; titanium dioxide, accounting for 25% of the mass of component A; carbon black, accounting for 0.05% of the mass of component A; anti-settling agent was polyamide wax, accounting for 0.5% of the mass of component A; defoaming agent, accounting for 0.5% of the mass of component A; leveling agent, accounting for 0.8% of the mass of component A; light stabilizer, which was bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. A mixture of methyl-4-piperidinyl) sebacate, accounting for 0.5% by weight of component A; a UV absorber, a hydroxyphenylbenzotriazole UV absorber, accounting for 0.8% by weight of component A; and a solvent, a mixture of propylene glycol methyl ether acetate, dimethyl sulfoxide, and xylene, accounting for 3% by weight of component A. The components are added sequentially under low-speed stirring until uniformly mixed, and then dispersed at a high speed of 2500 rpm / min, maintaining the temperature at 40°C for not less than 30 minutes, and the fineness is detected to be no higher than 50 μm to obtain component A with added additives;

[0123] (10) According to the weight of component A in step (9), the weight of the aqueous isocyanate is weighed, and the molar ratio of -NCO in the aqueous isocyanate and the molar ratio of -NH in component A are calculated as 1.2:1, and the two are fully stirred and mixed to obtain a heat storage coating.

[0124] Example 3

[0125] Step 1: preparing expanded graphite;

[0126] Weigh an appropriate amount of EG700 as the expanded graphite raw material, place it in a microwave oven, and microwave heat it at 800W for 2.5 minutes. Place the expanded graphite in a vacuum oven at 100°C (vacuum degree -0.07 to 0.1MPa) for 2 hours to obtain expanded graphite.

[0127] Step 2: Preparation of hydrated salt phase change material

[0128] 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, and the mixture was heated and stirred in a water bath at 55° C. until the mixture melted into a transparent liquid to obtain a hydrated salt phase change material.

[0129] Step 3: Preparation of heat storage microcapsules

[0130] The expanded graphite prepared in step 1 is added to the molten eutectic hydrated salt in step 2, wherein the mass fraction of the eutectic hydrated salt is 95% and the mass fraction of the expanded graphite is 5%. The two are mechanically stirred and mixed for 10 minutes to obtain a eutectic hydrated salt / graphite mixture.

[0131] Step 4: Preparation of heat storage coating

[0132] The mass proportion of the water-based polyaspartic acid ester polyurea base material is set to 50%, the mass proportion of the binder is set to 20%, and the mass proportion of the phase change filler is set to 30%.

[0133] (1) Polyetheramine and polyaspartic acid ester were weighed in a molar ratio of 1:3 and placed in a four-necked flask for vacuum drying; the vacuum drying conditions were: 100°C, -0.07 MPa, and time: 1 hour. In this embodiment, the polyetheramine was polyetheramine M1000, and the molar ratio of polyaspartic acid ester F420 to polyaspartic acid ester F520 in the polyaspartic acid ester was 4:1.

[0134] (2) Weigh diisocyanate at a molar ratio of polyetheramine to diisocyanate of 1:1 and place it in a constant pressure titration funnel. In this embodiment, the diisocyanate is hexamethylene diisocyanate.

[0135] (3) Place the binder and phase change filler in a constant pressure funnel respectively.

[0136] (4) The four-necked flask containing polyetheramine and polyaspartic acid ester in step (1) was taken out from a vacuum drying oven, nitrogen was introduced into the flask while the stirrer was turned on, and the temperature was lowered to 30°C.

[0137] (5) Open the constant pressure funnel containing the binder PTFE emulsion in step (3) and drop the binder into the four-necked flask in step (4). The addition time is 1 hour, and stirring is turned on at 40 r / min. After the addition is completed, stirring is stopped.

[0138] (6) Open the constant pressure funnel with the phase change filler in step (3), and add the phase change filler dropwise to the four-necked flask in step (5). The addition time is 1 hour, and stirring is turned on at 50 r / min. After the addition is completed, stirring is stopped.

[0139] (7) Open the constant pressure titration funnel in step (2) and add diisocyanate dropwise to the four-necked flask at a constant rate for 1 hour. The molar ratio of polyetheramine to diisocyanate is 1:1.1.

[0140] (8) After the dripping is completed, a certain amount of dipropylene glycol dimethyl ether is used to rinse the constant pressure titration funnel and drip into the four-necked flask, and the temperature is raised to 50 ° C and the reaction is kept at this temperature for 3 h.

[0141] (9) Replace the constant pressure titration funnel and slowly add deionized water to the reaction product of step (8) dropwise for 0.5 h, with a stirring speed of 1300 r / min and a stirring time of 0.3 h to obtain component A.

[0142] (10) Acrylic dispersant was added to the heat storage polyaspartic acid ester dispersion in sequence, accounting for 1.5% of the total mass fraction of component A; titanium dioxide, accounting for 30% of the mass of component A; carbon black, accounting for 0.1% of the mass of component A; anti-settling agent was polyamide wax, accounting for 1% of the mass of component A; defoaming agent, accounting for 1% of the mass of component A; leveling agent, accounting for 1% of the mass of component A; light stabilizer, which was bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8-(1,2,2,6,6-pentamethyl)-1-methyl-2-piperidinyl ... A mixture of propylene glycol methyl ether acetate, dimethyl sulfoxide and xylene, accounting for 1% of the mass of component A; a UV absorber, which is a hydroxyphenylbenzotriazole UV absorber, accounting for 1.2% of the mass of component A; and a solvent, which is a mixture of propylene glycol methyl ether acetate, dimethyl sulfoxide and xylene, accounting for 10% of the mass of component A. The components are added in sequence under low-speed stirring and mixed uniformly, and then dispersed at a high speed of 2500 rpm / min, maintaining the temperature at 40°C for not less than 30 minutes, and the fineness is detected to be no higher than 50 μm to obtain component A with added additives;

[0143] (11) According to the weight of component A in step (9), the weight of the aqueous isocyanate is weighed, and the molar ratio of -NCO in the aqueous isocyanate and the molar ratio of -NH in component A are calculated as 1.2:1, and the two are fully stirred and mixed to obtain a heat storage coating.

[0144] Example 4

[0145] Step 1: preparing expanded graphite;

[0146] Weigh an appropriate amount of EG800 as the expanded graphite raw material, place it in a microwave oven, and microwave heat it at a power of 800W for 3 minutes. Place the expanded graphite in a vacuum oven at 120°C (vacuum degree -0.07~0.1MPa) for 2 hours. After drying, expanded graphite is obtained.

[0147] Step 2: Preparation of hydrated salt phase change material

[0148] 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, and the mixture was heated and stirred in a water bath at 55° C. until the mixture melted into a transparent liquid to obtain a hydrated salt phase change material.

[0149] Step 3: Preparation of heat storage microcapsules

[0150] The expanded graphite prepared in step 1 is added to the molten eutectic hydrated salt in step 2, wherein the mass fraction of the eutectic hydrated salt is 95% and the mass fraction of the expanded graphite is 5%. The two are mechanically stirred and mixed for 15 minutes to obtain a eutectic hydrated salt / graphite mixture.

[0151] Step 4: Preparation of heat storage coating

[0152] The mass proportion of the water-based polyaspartic acid ester polyurea base material is set to 40%, the mass proportion of the binder is set to 30%, and the mass proportion of the phase change filler is set to 30%.

[0153] (1) Polyetheramine and polyaspartic acid ester were weighed in a molar ratio of 1:8 and placed in a four-necked flask for vacuum drying; the vacuum drying conditions were: 105°C, -0.04 MPa, and a time of 1.2 hours. In this embodiment, the polyetheramine was polyetheramine M200, and the molar ratio of polyaspartic acid ester F420 to polyaspartic acid ester F520 in the polyaspartic acid ester was 8:1.

[0154] (2) Weigh diisocyanate at a molar ratio of polyetheramine to diisocyanate of 1:1.3 and place it in a constant pressure titration funnel. In this embodiment, the diisocyanate is 4,4'-dicyclohexylmethane diisocyanate.

[0155] (3) Place the binder and phase change filler in a constant pressure funnel respectively.

[0156] (4) The four-necked flask containing polyetheramine and polyaspartic acid ester in step (1) was taken out from a vacuum drying oven, nitrogen was introduced into the flask while the stirrer was turned on, and the temperature was lowered to 50°C.

[0157] (5) Open the constant pressure funnel containing the binder PTFE emulsion in step (3) and drop the binder into the four-necked flask in step (4). The addition time is 2 hours, and stirring is turned on at 70 r / min. After the addition is completed, stirring is stopped.

[0158] (6) Open the constant pressure funnel with the phase change filler in step (3), and add the phase change filler dropwise to the four-necked flask in step (5). The addition time is 2 hours, and stirring is started at 60 r / min. After the addition is completed, stirring is stopped.

[0159] (7) Open the constant pressure titration funnel in step (2) and add diisocyanate dropwise to the four-necked flask at a constant rate for 1.5 hours. The molar ratio of polyetheramine to diisocyanate is 1:1.3.

[0160] (8) After the dripping is completed, a certain amount of dipropylene glycol dimethyl ether is used to rinse the constant pressure titration funnel and drip into the four-necked flask, and the temperature is raised to 70 ° C and the reaction is kept at this temperature for 2 h.

[0161] (9) Replace the constant pressure titration funnel and slowly add deionized water to the reaction product of step (8) dropwise for 1 h, with a stirring speed of 1000 r / min and a stirring time of 0.5 h to obtain component A.

[0162] (10) Acrylic dispersant was added to the heat storage polyaspartic acid ester dispersion in sequence, accounting for 1.3% of the total mass fraction of component A; titanium dioxide, accounting for 28% of the mass of component A; carbon black, accounting for 0.08% of the mass of component A; anti-settling agent was polyamide wax, accounting for 0.8% of the mass of component A; defoaming agent, accounting for 0.7% of the mass of component A; leveling agent, accounting for 0.9% of the mass of component A; light stabilizer, which was bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8-(1,2,2,6,6- A mixture of pentamethyl-4-piperidinyl) sebacate, accounting for 0.9% of the weight of component A; a UV absorber, a hydroxyphenylbenzotriazole UV absorber, accounting for 1.1% of the weight of component A; and a solvent, a mixture of propylene glycol methyl ether acetate, dimethyl sulfoxide, and xylene, accounting for 9% of the weight of component A. The components are added sequentially under low-speed stirring until uniformly mixed, and then dispersed at a high speed of 2500 rpm / min, maintaining the temperature at 40°C for not less than 30 minutes, and the fineness is detected to be no higher than 50 μm to obtain component A with added additives;

[0163] (11) According to the weight of component A in step (9), the weight of the aqueous isocyanate is weighed, and the molar ratio of -NCO in the aqueous isocyanate and the molar ratio of -NH in component A are calculated as 1.2:1, and the two are fully stirred and mixed to obtain a heat storage coating.

[0164] Example 5

[0165] Step 1: preparing expanded graphite;

[0166] Weigh an appropriate amount of EG800 as the expanded graphite raw material, place it in a microwave oven, and microwave heat it at a power of 800W for 3 minutes. Place the expanded graphite in a vacuum oven at 120°C (vacuum degree -0.07~0.1MPa) for 2 hours. After drying, expanded graphite is obtained.

[0167] Step 2: Preparation of hydrated salt phase change material

[0168] 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, and the mixture was heated and stirred in a water bath at 55° C. until the mixture melted into a transparent liquid to obtain a hydrated salt phase change material.

[0169] Step 3: Preparation of heat storage microcapsules

[0170] The expanded graphite prepared in step 1 is added to the molten eutectic hydrated salt in step 2, wherein the mass fraction of the eutectic hydrated salt is 95% and the mass fraction of the expanded graphite is 5%. The two are mechanically stirred and mixed for 15 minutes to obtain a eutectic hydrated salt / graphite mixture.

[0171] Step 4: Preparation of heat storage coating

[0172] The mass proportion of the water-based polyaspartic acid ester polyurea base material is set to 40%, the mass proportion of the binder is set to 20%, and the mass proportion of the phase change filler is set to 40%.

[0173] (1) Polyetheramine and polyaspartic acid ester were weighed in a molar ratio of 1:8 and placed in a four-necked flask for vacuum drying; the vacuum drying conditions were: 105°C, -0.04 MPa, and a time of 1.2 hours. In this embodiment, the polyetheramine was polyetheramine M200, and the molar ratio of polyaspartic acid ester F420 to polyaspartic acid ester F520 in the polyaspartic acid ester was 5:1.

[0174] (2) Weigh diisocyanate at a molar ratio of polyetheramine to diisocyanate of 1:1.3 and place it in a constant pressure titration funnel. In this embodiment, the diisocyanate is 4,4'-dicyclohexylmethane diisocyanate.

[0175] (3) Place the binder and phase change filler in a constant pressure funnel respectively.

[0176] (4) The four-necked flask containing polyetheramine and polyaspartic acid ester in step (1) was taken out from a vacuum drying oven, nitrogen was introduced into the flask while the stirrer was turned on, and the temperature was lowered to 50°C.

[0177] (5) Open the constant pressure funnel containing the binder PTFE emulsion in step (3) and drop the binder into the four-necked flask in step (4). The addition time is 2 hours, and stirring is turned on at 40 r / min. After the addition is completed, stirring is stopped.

[0178] (6) Open the constant pressure funnel with the phase change filler in step (3), and add the phase change filler dropwise to the four-necked flask in step (5). The addition time is 2 hours, and stirring is started at 50 r / min. After the addition is completed, stirring is stopped.

[0179] (7) Open the constant pressure titration funnel in step (2) and add diisocyanate dropwise to the four-necked flask at a constant rate for 1.5 hours. The molar ratio of polyetheramine to diisocyanate is 1:1.3.

[0180] (8) After the dripping is completed, a certain amount of dipropylene glycol dimethyl ether is used to rinse the constant pressure titration funnel and drip into the four-necked flask, and the temperature is raised to 70 ° C and the reaction is kept at this temperature for 2 h.

[0181] (9) Replace the constant pressure titration funnel and slowly add deionized water to the reaction product of step (8) dropwise for 1 h, with a stirring speed of 1000 r / min and a stirring time of 0.3 h to obtain component A.

[0182] (10) Acrylic dispersant was added to the heat storage polyaspartic acid ester dispersion in sequence, accounting for 1.5% of the total mass fraction of component A; titanium dioxide, accounting for 27% of the mass of component A; carbon black, accounting for 0.1% of the mass of component A; anti-settling agent was polyamide wax, accounting for 1% of the mass of component A; defoaming agent, accounting for 1% of the mass of component A; leveling agent, accounting for 0.8% of the mass of component A; light stabilizer, which was bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-methyl-8-(1,2,2,6,6-pentamethyl)-4-piperidinyl) sebacate. A mixture of methyl-4-piperidinyl) sebacate, accounting for 1% by weight of component A; a UV absorber, a hydroxyphenylbenzotriazole UV absorber, accounting for 1% by weight of component A; and a solvent, a mixture of propylene glycol methyl ether acetate, dimethyl sulfoxide, and xylene, accounting for 10% by weight of component A. The components are added sequentially under low-speed stirring until uniformly mixed, and then dispersed at a high speed of 2500 rpm / min, maintaining the temperature at 40°C for not less than 30 minutes, and the fineness is detected to be no higher than 50 μm to obtain component A with added additives;

[0183] (11) According to the weight of component A in step (9), the weight of the aqueous isocyanate is weighed, and the molar ratio of -NCO in the aqueous isocyanate and the molar ratio of -NH in component A are calculated as 1.2:1, and the two are fully stirred and mixed to obtain a heat storage coating.

[0184] 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 in the scope of protection of the present invention.

Claims

1. An anti-icing heat storage film suitable for wind turbine blades, characterized in that: The invention comprises a hollow glass fiber cloth arranged on the outside of a wind turbine blade, and a heat storage protective film is arranged on the outside of the hollow glass fiber cloth; the wind turbine blade and the hollow glass fiber cloth are bonded by an adhesive coating, and the hollow glass fiber cloth and the heat storage protective film are bonded by an adhesive coating; the thickness of the heat storage protective film is 200 μm to 500 μm; The bonding coating is a polyurethane-modified epoxy resin, and hollow microspheres are added to the polyurethane-modified epoxy resin; The heat storage protective film comprises a water-based polyaspartic acid ester polyurea base resin, a binder, heat storage microcapsules and additives; the binder is a PTFE water-based emulsion; the heat storage microcapsules are dispersed in the water-based polyaspartic acid ester polyurea base resin; The heat storage microcapsule is composed of expanded graphene and a hydrated salt phase change material, the hydrated salt phase change material is filled in the pores of the expanded graphene, and the hydrated salt phase change material is composed of dipotassium hydrogen phosphate hexahydrate, glycine and disodium hydrogen phosphate dodecahydrate; The water-based polyaspartic acid ester polyurea base resin consists of a heat-storage polyaspartic acid ester dispersion and water-based isocyanate. The heat-storage polyaspartic acid ester dispersion consists of polyetheramine, polyaspartic acid ester and diisocyanate.

2. The anti-icing heat storage film suitable for wind turbine blades according to claim 1, characterized in that: The addition amount of the hollow microspheres is 4.5% to 6.0 wt% of the mass of the polyurethane-modified epoxy resin.

3. The anti-icing heat storage film suitable for wind turbine blades according to claim 1, characterized in that: Calculated by mass fraction, the particle size distribution of the hollow microspheres added to the polyurethane-modified epoxy resin is as follows: 270-325 mesh accounts for 20%, 500-600 mesh accounts for 60%, and 800-1250 mesh accounts for 20%.

4. The anti-icing heat storage film suitable for wind turbine blades according to claim 1, characterized in that: In terms of mass fraction, the water-based polyaspartic acid ester polyurea base resin in the heat storage protective film accounts for 40%~50%, the binder accounts for 20%~30%, and the heat storage microcapsules account for 20%~40%.

5. The anti-icing heat storage film suitable for wind turbine blades according to claim 1, characterized in that: The additives include dispersant, titanium dioxide, carbon black, anti-settling agent, defoaming agent, leveling agent, light stabilizer and solvent.

6. A method for preparing an anti-icing heat storage film suitable for wind turbine blades according to claim 1, characterized in that: The following steps are involved: Applying an adhesive on the polished wind turbine blade substrate, placing a hollow glass fiber cloth on the adhesive, applying an adhesive on the hollow glass fiber cloth, and placing a heat storage protective film on the adhesive; The preparation method of the heat storage protective film comprises the following steps: Step 1: adding a hydrated salt phase change material to expanded graphene and stirring to obtain a heat storage microcapsule suspension; Step 2, adding PTFE emulsion dropwise to the mixture of polyetheramine and polyaspartic acid ester, stirring evenly after the addition, to obtain process mixture 1; Step 3, adding the heat storage microcapsule suspension to the process mixture 1 dropwise, stirring evenly to obtain the process mixture 2; Step 4, adding diisocyanate dropwise to the process mixture 2 to obtain the process mixture 3; Step 5, adding water dropwise to the mixture of process 3 and stirring evenly to obtain component A; Step 6, adding additives to component A; Step 7, adding aqueous isocyanate dropwise to component A with the additive, and stirring evenly to obtain a heat storage coating; Step 8: Vacuum-infuse the heat storage coating into a film-making mold, and form a film after solidification to obtain a heat storage protective film.

7. The method for preparing an anti-icing heat storage film suitable for wind turbine blades according to claim 6, characterized in that: In step 1, the preparation process of the hydrated salt phase change material is as follows: dipotassium hydrogen phosphate hexahydrate, glycine and disodium hydrogen phosphate dodecahydrate are mixed in a mass ratio of 176.67:13.86:0.99, placed in a 55°C water bath, heated and stirred until melted into a transparent liquid, to obtain a hydrated salt phase change material.

8. The method for preparing an anti-icing heat storage film suitable for wind turbine blades according to claim 7, characterized in that: In step 2, the polyaspartic acid ester is a mixture of polyaspartic acid ester F420 and polyaspartic acid ester F520 in a molar ratio of (4-5):

1.

9. The method for preparing an anti-icing heat storage film suitable for wind turbine blades according to claim 8, characterized in that: In step 2, the mass ratio of the polyaspartic acid ester to the polyetheramine is (3-8):

1.

10. The method for preparing an anti-icing heat storage film suitable for wind turbine blades according to claim 9, characterized in that: The molar ratio of the diisocyanate added in step 4 to the polyetheramine in step 2 is (1-1.3):1; In step 7, the molar ratio of -NH in component A to -NCO in the aqueous isocyanate is 1:1.2.

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