Fluorocarbon modified water-based thermal insulation waterproof curing coating and application thereof

Abstract

This invention provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating and its application, belonging to the field of waterborne functional coatings technology. The coating comprises a fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion, hollow glass microspheres, silica aerogel powder, a UV initiator, a room temperature moisture curing crosslinking agent, additives, and deionized water. The hollow glass microspheres and aerogel powder construct a multi-level pore structure in the coating, effectively inhibiting heat conduction and convection, giving the coating low thermal conductivity. Fluorocarbon segments migrate to the surface, giving the coating durable hydrophobicity and self-cleaning properties. Curing employs a combination of UV surface setting and deep moisture crosslinking, solving the problem of thick coatings being difficult to cure completely in one step. This coating uses water as the dispersion medium, has extremely low volatile organic compound content, is easy to apply, and is suitable for thermal insulation and waterproofing of building exterior walls, roofs, industrial storage tanks, and pipelines.

Description

Technical Field

[0001] This invention relates to the field of water-based functional coatings, specifically to a fluorocarbon-modified water-based thermal insulation, waterproofing, and curing coating and its application. Background Technology

[0002] The external envelope of buildings and industrial facilities faces two major challenges during long-term use: heat transfer and moisture infiltration. Sunlight causes exterior walls and roofs to continuously absorb heat, which is then conducted into the interior, increasing cooling energy consumption. In winter, indoor heat is lost outwards through the envelope, increasing the heating load. Simultaneously, rainwater, snowmelt, and condensation continuously erode the surface of the substrate. Moisture seeps into the walls or metal components, causing a series of secondary problems such as steel corrosion, concrete carbonization, freeze-thaw damage, and mold growth, severely weakening the structural load-bearing capacity and thermal performance.

[0003] To address these issues, engineering projects typically employ two independent structural systems: thermal insulation and waterproofing. The insulation layer is often assembled from materials such as rock wool boards, extruded polystyrene boards, or polyurethane foam boards, while the waterproofing layer is applied separately using asphalt membrane, polymer membrane, or waterproof coating. This composite approach has significant drawbacks: the materials lack chemical bonding, relying solely on physical overlapping or mechanical fixation. The interlayer interfaces are prone to peeling and blistering under temperature fluctuations and building settlement. Once the external waterproofing layer experiences localized damage, moisture flows and diffuses along the interface, causing a sharp increase in thermal conductivity in large areas of the insulation layer after it becomes damp, severely reducing its insulation effect and making repairs difficult. Replacing damaged insulation and waterproofing layers requires peeling off each layer individually, a cumbersome process with high repair costs. Furthermore, traditional insulation materials like rock wool boards generate a lot of dust, which can affect worker health during construction, and the cutting of these materials produces substantial construction waste.

[0004] Regarding waterproof coatings, existing water-based coatings mostly rely on simple physical drying or thermal cross-linking to form a film, which generally suffers from slow curing speed, poor initial water resistance, and difficulty in complete curing of thick coatings. Although solvent-based coatings form a film faster, they contain a large amount of volatile organic compounds, causing environmental pollution during construction and use, and their use is limited in enclosed spaces and poorly ventilated areas.

[0005] In the field of thermal insulation coatings, some products reduce thermal conductivity by introducing hollow fillers. However, insufficient compatibility between the fillers and the resin matrix often leads to filler floating or settling, resulting in uneven thermal insulation performance across the coating. Furthermore, coatings relying solely on physical film formation lack density, allowing water vapor and molecules to slowly penetrate, leading to gradual deterioration of insulation performance under prolonged humid conditions. Therefore, this paper proposes a water-based coating that integrates thermal insulation, heat preservation, and waterproofing functions, boasts rapid curing, and is environmentally friendly. Summary of the Invention

[0006] The present invention aims to solve the problems mentioned in the background art by providing a fluorocarbon modified water-based thermal insulation and waterproof curing coating and its application.

[0007] The specific technical solution is as follows: A fluorocarbon-modified waterborne thermal insulation and waterproof curing coating, by weight, comprises 30-60 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion, 5-20 parts of hollow glass microspheres, 3-12 parts of silica aerogel powder, 0.5-3 parts of ultraviolet photoinitiator, 1-6 parts of room temperature moisture curing crosslinking agent, 1-5 parts of additives, and 10-35 parts of deionized water; The fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion is prepared by emulsion copolymerization of fluorinated acrylate monomers and polyurethane prepolymers. The fluorinated acrylate monomers are acrylate monomers containing at least one of perfluorohexyl or perfluorobutyl, and the copolymer emulsion contains olefinic unsaturated double bonds that can be polymerized by free radicals. The residual amount of olefinic unsaturated double bonds in the copolymer emulsion is ensured by controlling the copolymerization conversion rate to 70-90% or by adding polyfunctional acrylate monomers after copolymerization, so that its iodine value is not less than 5 mgI2 / g dry polymer.

[0008] Fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion is used as the main film-forming agent. The perfluoroalkyl segments migrate to the surface during film formation, significantly reducing the surface energy and providing durable hydrophobicity and stain resistance. The polymerizable unsaturated double bonds retained in the emulsion skeleton provide crosslinking sites for the photocuring reaction, enabling the coating to rapidly form a dense surface layer under UV irradiation. Hollow glass microspheres and silica aerogel powder work synergistically to construct numerous micro- and nano-scale cavities and pores within the coating, effectively blocking solid-phase heat conduction and suppressing air convection heat transfer, thus endowing the coating with excellent thermal insulation capabilities. A UV photoinitiator, combined with photocuring groups, achieves rapid surface setting, while a room-temperature moisture-curing crosslinking agent utilizes ambient moisture to initiate a post-crosslinking reaction, allowing the coating to gradually achieve overall curing. This dual curing mechanism solves the problem of thick coatings being difficult to cure completely in one step, improving construction efficiency while ensuring coating density. The system uses water as the dispersion medium, with extremely low volatile organic compound (VOC) content, making the construction process environmentally friendly.

[0009] The preparation of the fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion includes the following steps: S1: Polyether diol or polyester diol, hydrophilic chain extender, and diisocyanate are mixed at an NCO / OH molar ratio of 1.2–2.0:1 and reacted at 60–85°C for 1.5–3 h in the presence of dibutyltin dilaurate catalyst; then, a hydroxyl-containing olefinic unsaturated monomer is added, and the reaction is continued for 0.5–1 h to obtain an isocyanate-terminated polyurethane prepolymer containing olefinic unsaturated double bonds; wherein the diisocyanate is selected from hexamethylene diisocyanate, isophorone diisocyanate, and toluene diisocyanate. The product contains at least one isocyanate; the hydrophilic chain extender is selected from at least one of dimethylolpropionic acid and dimethylolbutyric acid, and its amount is 2-8% of the weight of polyether diol or polyester diol; the hydroxyl-containing olefinic unsaturated monomer is selected from at least one of hydroxyethyl methacrylate and hydroxyethyl acrylate, and its amount is 1-5% of the weight of polyether diol or polyester diol; the amount of the catalyst is 0.01-0.5% of the total weight of polyether diol or polyester diol, hydrophilic chain extender and diisocyanate. S2: Add fluorinated acrylate monomers and acrylate hard and soft segment monomers to the polyurethane prepolymer. The amount of fluorinated acrylate monomers is 5-30% of the total weight of the fluorinated acrylate monomers and acrylate hard and soft segment monomers, and the amount of acrylate hard and soft segment monomers is 70-95% of the total weight of the fluorinated acrylate monomers and acrylate hard and soft segment monomers. The acrylate hard and soft segment monomers are selected from at least one of butyl acrylate and methyl methacrylate. Stir until homogeneous. Add a neutralizing agent to adjust the pH to 6.5-7.5. The neutralizing agent is selected from at least one of triethylamine and ammonia water, and its amount is 0.9-1.1 times the molar amount of the hydrophilic chain extender. Stir at high speed of 1000-3000 rpm. Add deionized water under stirring to emulsify and disperse, obtaining an emulsion; then add a water-soluble initiator to the emulsion, and carry out an emulsion copolymerization reaction at 70-90°C, controlling the reaction time to ensure a total monomer conversion rate of 70-90%, or after the conversion rate reaches 90% or more, add 0.5-2% of a multifunctional acrylate monomer (selected from trimethylolpropane triacrylate and pentaerythritol triacrylate) according to the total weight of the monomers and continue the reaction for 10-30 minutes to obtain the fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion; the water-soluble initiator is selected from at least one of ammonium persulfate and potassium persulfate, and its amount is 0.1-1.0% of the total weight of the fluorinated acrylate monomer and the acrylate soft and hard segment monomers.

[0010] In the polyurethane prepolymerization stage, polymerizable double bonds are introduced through hydroxyl-containing olefinic unsaturated monomers. This allows for the formation of interpenetrating or grafted structures around the polyurethane chains during subsequent copolymerization of acrylate monomers. This structure combines the elasticity of polyurethane with the hardness and weather resistance of acrylate, resulting in a film that is less prone to cracking after formation. Hydrophilic chain extenders provide carboxyl groups to the prepolymer side chains, which, after neutralization, endow the polymer with self-emulsifying capabilities. Stable emulsions can be obtained without the addition of external emulsifiers, reducing the coating's sensitivity to moisture. Fluorinated acrylate monomers participate in the copolymerization reaction, fixing the perfluoroalkyl chains to the polymer backbone through chemical bonds. Compared to physical blending, this results in stronger anti-migration properties and a more durable hydrophobic effect. The entire preparation pathway allows for precise control of the double bond and fluorine content in the emulsion, laying a uniform reaction foundation for subsequent dual crosslinking through photocuring and moisture curing.

[0011] The specific method for controlling free monomers at a conversion rate of 70-90% is as follows: This invention retains polymerizable olefinic unsaturated double bonds by controlling the copolymerization conversion rate to 70-90%, while employing multiple technical means to control the total amount of free monomers in the system below 1.0 wt%, thus ensuring the storage stability and low VOC characteristics of the coating: 1. Segmented initiation and temperature gradient control The emulsion copolymerization reaction is divided into two stages: the first stage involves reacting at 70–75°C until the monomer conversion reaches 50–60%, at which point approximately 60–70% of the initiator is consumed; the second stage involves raising the temperature to 80–90°C and continuing the reaction until the target conversion reaches 70–90%, and holding at this temperature for 15–30 minutes. This process allows the initiator to decompose gradually, avoiding explosive polymerization caused by excessively high local monomer concentrations, while ensuring that most of the unreacted monomers participate in polymerization during the holding stage, reducing the free monomer content by 40–60%.

[0012] 2. Oxidation-reduction elimination system Once the target conversion rate is reached, a redox initiator combination (tert-butyl hydroperoxide / sodium formaldehyde bisulfite, molar ratio 1:1.2) is added to the emulsion at 0.05–0.2% of the total monomer weight, and the reaction is carried out at 50–60°C for 30–60 minutes. This system can efficiently initiate the polymerization of residual monomers at low temperatures, further reducing the free monomer content to below 0.5 wt%, without significantly consuming the retained olefinic unsaturated double bonds (iodine value decrease ≤5%).

[0013] 3. Vacuum removal process Before the emulsion is discharged, it is degassed at 50–60°C and a vacuum of -0.08–-0.09 MPa for 15–30 minutes to remove residual volatile monomers and low-boiling-point byproducts from the system. This process can control the final total amount of free monomers to below 0.3 wt% without affecting the stability and double bond content of the emulsion.

[0014] 4. Addition of trace amounts of polymerization inhibitors After degassing, add a polymerization inhibitor (p-hydroxyanisole or 2,6-di-tert-butyl-p-cresol) at 0.005–0.02% of the total monomer weight to the emulsion. The polymerization inhibitor effectively inhibits the self-polymerization reaction of free monomers during storage, ensuring that the viscosity change rate of the emulsion is ≤15% and the iodine value decrease is ≤8% after 6 months of storage at room temperature, thus ensuring the stability of the coating's pot life and curing performance.

[0015] By using the above method, this invention controls the total amount of free monomers in the system to an extremely low level while retaining enough polymerizable double bonds (iodine value ≥ 5 mg I2 / g polymer), fundamentally solving the storage stability problem and VOC exceeding risk that may be caused by low conversion rate processes.

[0016] The true density of the hollow glass microspheres is 0.12–0.45 g / cm³. 3 The particle size D50 is 10–80 μm, and the thermal conductivity is 0.03–0.08 W / (m·K); the specific surface area of ​​the silica aerogel powder is 500–1000 m². 2 / g, with an average pore size of 5–50 nm.

[0017] The low true density of hollow glass microspheres indicates a large proportion of internal cavities, allowing for the introduction of numerous enclosed gas spaces with relatively light filler mass, thus effectively reducing the volumetric thermal conductivity of the coating. The selected particle size range facilitates uniform spreading of the microspheres in the coating, preventing them from floating on the surface or agglomerating and settling, contributing to the formation of a uniform and continuous thermal insulation structure. The high specific surface area and nanoscale pore size of silica aerogel powder result in extremely low solid-phase thermal conductivity and suppress the thermal motion of gas molecules through the nanopore wall effect. This complements the micron-sized hollow glass microspheres on a scale, together forming a multi-level porous thermal insulation framework that weakens heat transfer from multiple dimensions, giving the final coating outstanding thermal insulation performance.

[0018] The ultraviolet photoinitiator is selected from one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide; the room temperature moisture curing crosslinking agent is a compound containing an alkoxysilyl group, or a blocked aqueous polyisocyanate (this blocked aqueous polyisocyanate needs to be deblocked by heating at 80-120°C before it can be cured at room temperature moisture, and its specific usage is described in the curing method section below); the deblocking temperature of the blocked aqueous polyisocyanate is 80-120°C, and it is selected from one or more of dimethylpyrazole-blocked hexamethylene diisocyanate trimer and diethyl malonate-blocked isophorone diisocyanate trimer; the compound containing an alkoxysilyl group is selected from one or more of 3-methacryloyloxypropyltrimethoxysilane and 3-glycidyl etheroxypropyltrimethoxysilane.

[0019] The selected UV initiator exhibits high initiation efficiency under UV irradiation in the specified wavelength range, rapidly generating free radicals and driving unsaturated double bond crosslinking. This allows the coating to complete surface curing within a very short irradiation time, resulting in rapid loss of tackiness. The alkoxysilane-containing crosslinking agent undergoes hydrolysis and condensation after the coating absorbs ambient moisture. The resulting siloxane network increases the crosslinking point density of the coating, improving hardness and scratch resistance. Simultaneously, the residual silanol groups can form chemical bonds with the inorganic substrate surface, enhancing adhesion. The blocked polyisocyanate is inert at room temperature, and its unsealing temperature range facilitates storage and transportation. Furthermore, it can release free isocyanate groups through gentle heating after application. These groups react with active hydrogen and moisture in the coating to complete deep crosslinking, overcoming the limited penetration depth of simple UV curing and enabling the overall hardening of thick coatings.

[0020] The additives include the following sub-components in parts by weight of the total coating: 0.1 to 1.0 parts dispersant, 0.1 to 0.5 parts defoamer, 0.1 to 0.8 parts leveling agent, 0.1 to 0.5 parts thickener, 0.05 to 0.2 parts mildew inhibitor, and 0.5 to 2.0 parts film-forming aid.

[0021] Dispersants adsorb onto the surface of filler particles, generating electrostatic or steric repulsion, allowing hollow glass microspheres and silica aerogel powder to remain stably suspended without flocculation, thus preventing uneven thermal insulation effects caused by uneven filler distribution. Defoamers quickly break up air bubbles introduced during production mixing and application, preventing pinholes or crater-like defects after coating drying. Leveling agents adjust the surface tension driving force of the coating, promoting rapid leveling of the wet film and eliminating brush or roller marks for a smooth, even finish. Thickeners impart suitable low shear viscosity and thixotropy to the system, preventing hard settling of fillers during storage and providing good anti-sagging properties during application. Antifungal agents inhibit mold growth in humid environments, extending the coating's lifespan in applications such as building exteriors. Film-forming aids lower the deformation and fusion temperatures of latex particles, helping the coating form a continuous, dense film over a wider temperature range, enhancing its sealing and adhesion.

[0022] The coating undergoes a dual curing process, comprising: if a blocked waterborne polyisocyanate crosslinking agent is used, firstly, heating at 80–120°C for 5–30 minutes to deblock the crosslinking agent; then, ultraviolet radiation curing is performed, with an ultraviolet wavelength of 320–400 nm and an irradiation energy of 500–2000 mJ / cm². 2 This process forms a dense, waterproof layer on the coating surface. Finally, room temperature moisture curing is performed. Under conditions of 30%–90% humidity and 5–40°C, the room temperature moisture curing crosslinking agent reacts with moisture to achieve deep crosslinking and curing within the coating. It should be noted that although the surface layer formed after UV curing is dense, it still possesses micron-level pores, or a certain water vapor transmission rate (not less than 10 g / (m²)) can be maintained by selecting some hydrophilic photocurable monomers (such as polyethylene glycol diacrylate). 2 • 24h) to ensure that ambient moisture can diffuse into the coating and trigger deep moisture cross-linking. Alternatively, a gradient curing strategy can be adopted: first, low-energy ultraviolet irradiation (300-500 mJ / cm²) is applied. 2 Only allow the surface layer to partially cure. After the moisture has mostly cured, apply high-energy ultraviolet light (1000-2000 mJ / cm²). 2 The final surface densification is then completed.

[0023] Pre-heating deblocks the coating containing blocked polyisocyanates, releasing some active isocyanate groups before UV irradiation, thus providing reserve reaction sites for subsequent crosslinking. Subsequent UV irradiation causes the polymer network containing double bonds on the surface to crosslink and solidify within seconds. The resulting dense skin layer not only provides an immediate waterproof barrier but also slows down the rapid evaporation of internal moisture, preserving the necessary moisture environment for moisture curing. The final room-temperature moisture curing stage relies on the slow, driven hydrolysis and condensation of alkoxysilanes or the reaction between isocyanates and water by air humidity. The crosslinking reaction progresses gradually from the coating surface inwards, ultimately forming a uniformly crosslinked coating without internal stress, avoiding the risks of insufficient curing or cracking that may occur with a single curing method.

[0024] The coating, after curing, has a thermal conductivity of 0.03–0.06 W / (m·K), a water contact angle greater than 120°, and an adhesion rating of 0–1 according to the cross-cut adhesion test.

[0025] The cured coating exhibits extremely low thermal conductivity due to the dense micro-nano-scale insulating units constructed by the hollow glass microspheres and aerogel powder, which create multi-level barriers to heat conduction and convection. The water contact angle on the coating surface exceeds 120 degrees, demonstrating significant hydrophobic properties. This stems from the directional migration of fluorinated segments during film formation and the synergistic effect of the siloxane crosslinking network, which significantly reduces the surface energy of the coating, making it difficult for rainwater to penetrate and spread, thus achieving highly efficient waterproofing and self-cleaning effects. It achieved the highest level in the cross-cut adhesion test, indicating that the crosslinking system within the coating provides strong adhesion between the coating and the substrate, and the interpenetrating network of the polyurethane-acrylate skeleton and the moisture-curing product effectively inhibits cohesive failure and interfacial delamination of the coating.

[0026] The room temperature moisture curing crosslinking agent is a combination of 3-methacryloyloxypropyltrimethoxysilane and dimethylpyrazole-blocked hexamethylene diisocyanate trimer, with a weight ratio of 1:0.3 to 1:3.

[0027] By combining 3-methacryloyloxypropyltrimethoxysilane with a dimethylpyrazole-blocked hexamethylene diisocyanate trimer, the methacryloyloxy group in the silane molecule can participate in UV-induced free radical crosslinking, anchoring it in the photocurable network. Meanwhile, the alkoxysilane portion undergoes hydrolysis and condensation in moisture, forming siloxane crosslinking sites. The trifunctional isocyanate released after the blocked polyisocyanate is unblocked further extends the chain and crosslinks. The two react sequentially at different stages, constructing a hybrid network integrating photocuring, moisture curing, and thermal deblocking crosslinking, significantly increasing the crosslinking density. The flexible structure of the siloxane also buffers the brittleness caused by isocyanate crosslinking, allowing the coating to maintain high hardness and strength while retaining good flexibility and impact resistance. The appropriate weight ratio ensures a synergistic match between the two crosslinking mechanisms, preventing one from excessively consuming active groups and causing incomplete reaction of the other.

[0028] The hollow glass microspheres and / or silica aerogel powder are subjected to surface hydrophobic modification treatment with a silane coupling agent, wherein the silane coupling agent is selected from one or more of hexamethyldisilazane, methyltrimethoxysilane, and dimethyldimethoxysilane.

[0029] After hydrophobic modification of the filler surface using a silane coupling agent, the silanol groups on the surface of hollow glass microspheres and aerogel powder are replaced by inert alkyl or silanyl groups, significantly reducing hydrophilicity. This makes the filler less prone to moisture absorption and clumping during storage and coating formulation, while also improving the compatibility and interfacial bonding between the filler and the fluorocarbon modified polymer matrix. The hydrophobic filler in the coating can prevent moisture penetration along the filler-resin interface, avoiding an increase in thermal conductivity and a decrease in adhesion due to interfacial water immersion. This maintains stable thermal insulation and waterproofing performance under humid conditions, and further enhances the overall hydrophobic durability of the coating.

[0030] The coating is applied by spraying, scraping, or rolling. The pot life of the coating at 25°C is 2–8 hours (the pot life is determined by the following method: the coating is sealed and placed at a constant temperature of 25°C, and every 0.5 hours it is taken out, stirred evenly, and the viscosity of the Forecast-4 cup is measured. The time when the viscosity increases to twice the initial viscosity is the end of the pot life). The surface drying time is 15–60 minutes (the surface drying time is determined by the cotton ball method in GB / T1728-1979, and the test conditions are 25°C and 50% relative humidity).

[0031] The coating is adaptable to various application methods such as spraying, scraping, and roller coating, exhibiting excellent thixotropic and rheological properties. It can meet the needs of different substrate shapes and site conditions, offering high efficiency for large-area application and minimizing sagging. Its long pot life at room temperature means that the viscosity of the prepared coating increases slowly within several hours, allowing for normal application and providing ample operating time for continuous work and intermittent stops, reducing material waste. The short surface drying time indicates that the coating can quickly form a dust-free solid surface after UV irradiation or moisture evaporation, helping to resist wind and sand pollution during outdoor construction and shortening the waiting interval for subsequent processes, thus accelerating project progress.

[0032] The volatile organic compound content of the coating is 0-50 g / L.

[0033] The coating formulation uses water as the primary diluent, and the introduction of organic solvents in the synthesis and formulation of resins and crosslinking agents is minimized, resulting in extremely low levels of volatile organic compounds (VOCs), far lower than the emissions of traditional solvent-based thermal insulation coatings. Very few harmful substances are released into the atmosphere during application and curing, complying with stringent environmental regulations. It is particularly suitable for use in poorly ventilated indoor spaces, underground areas, or locations with strict air quality requirements, and has minimal impact on the health of construction workers.

[0034] According to the national standard GB / T23986-2009 "Determination of Volatile Organic Compound (VOC) Content in Paints and Varnishes", the volatile organic compound content of the coating of this invention is 12-38 g / L, which is far lower than the requirement of ≤120 g / L for VOC content in water-based wall coatings stipulated in the national standard GB18582-2020 "Limits of Harmful Substances in Wall Coatings for Buildings", and also meets the most stringent green building coating standards.

[0035] The application of the fluorocarbon-modified water-based thermal insulation and waterproof curing coating on metal substrates, such as steel or aluminum alloys, involves directly applying the coating to the substrate surface without the need for a pre-priming primer. This coating achieves strong adhesion directly to the steel or aluminum alloy surface, eliminating the need for traditional anti-rust primers or phosphating treatments. This is due to the chemical adsorption of the abundant urethane, urea, and carboxyl groups on the fluorocarbon-modified polyurethane-acrylate copolymer molecular chain onto the metal surface, as well as the chemical bonding between the siloxane or isocyanate groups and the hydroxyl groups on the metal surface during the moisture curing stage. Eliminating the primer step simplifies the construction process, reduces material costs and labor input, and eliminates potential interlayer adhesion problems between the primer and topcoat, resulting in higher reliability of the entire coating system.

[0036] The fluorocarbon-modified water-based thermal insulation and waterproof curing coating is used for thermal insulation and waterproof coating of building exterior walls, roofs, corrugated steel roofs, and the outer walls of industrial storage tanks or pipelines. When applied to the exterior of these buildings and industrial facilities, the cured coating exhibits both low thermal conductivity and strong hydrophobic properties, significantly reducing the transfer of solar radiation heat into the building interior, lowering cooling energy consumption, and inhibiting heat loss in winter, thus providing thermal insulation and energy saving. The strong hydrophobic surface causes rainwater and dew to roll off as droplets, preventing prolonged retention and thus preventing moisture penetration into the substrate, which could lead to corrosion, frost heave damage, and decreased insulation performance. For metal materials such as corrugated steel sheets and storage tanks, the coating also provides an additional anti-corrosion barrier, slowing down the corrosion process of the substrate and extending the service life of the facility.

[0037] The application of the fluorocarbon-modified water-based thermal insulation and waterproof curing coating on concrete substrates involves directly applying the coating to the concrete surface. After curing, it forms an integrated coating that combines thermal insulation and waterproofing functions, replacing separate insulation and waterproofing layers. Direct application to the concrete surface results in an integrated coating that simultaneously provides thermal insulation, waterproofing, and moisture barrier properties, replacing the traditional composite structure of separately laid insulation boards and waterproof membranes. This integrated design eliminates the physical interface between the insulation and waterproofing layers, fundamentally eliminating the risk of system failure due to interlayer water ingress, blistering, and peeling. It also enhances structural integrity and durability. Furthermore, it reduces wet application processes and material types, lowering overall costs and structural loads, making it particularly suitable for energy-saving renovations of existing buildings where strict requirements on additional weight and construction thickness are necessary.

[0038] This invention also provides a method for preparing a fluorocarbon-modified water-based thermal insulation and waterproof curing coating, comprising the following steps: Step (a): Weigh each component according to the above weight ratio; Step (b): Mix the fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion with deionized water and additives, and stir at 300-800 rpm for 10-30 min to obtain a uniform slurry; Step (c): Add hollow glass microspheres and silica aerogel powder to the slurry obtained in step (b), and stir at 200-500 rpm for 20-60 min until the filler is evenly dispersed; Step (d): First, add the ultraviolet photoinitiator to the mixture obtained in step (c), stir evenly, then add the room temperature moisture curing crosslinking agent, and stir at 100-300 rpm for 5-15 minutes to obtain the fluorocarbon modified water-based thermal insulation and waterproof curing coating.

[0039] The preparation method first involves premixing the emulsion with water and various additives into a homogeneous liquid phase, creating a favorable wetting and dispersion environment for subsequent filler addition. Then, hollow glass microspheres and aerogel powder are added at a low rotation speed. This effectively avoids damage to the thin-walled structure of the microspheres due to high shear, maintaining their intact closed-cell morphology and ensuring undiminished thermal insulation performance. Simultaneously, the powder is fully coated and wetted by the slurry, achieving uniform suspension. Finally, after the system is fully mixed and the temperature is normal, a UV photoinitiator and a moisture-curing crosslinking agent are added, and the mixture is briefly mixed at an even lower rotation speed. This prevents the active components from prematurely reacting or deactivating under prolonged high shear or high temperature conditions, maximizing the preservation of the coating's chemical reaction potential and application stability during storage.

[0040] The present invention has the following beneficial effects: In terms of thermal insulation, the multi-level porous structure constructed from hollow glass microspheres and aerogel powder effectively suppresses both solid-state heat conduction and gas-state convection heat transfer simultaneously, resulting in an extremely low thermal conductivity of the cured coating. When applied to building exteriors or roofs, it significantly reduces heat transfer from solar radiation into the interior and heat loss from the interior during winter, thus lowering HVAC energy consumption. For industrial storage tanks and pipelines, the coating reduces heat loss or external heat intrusion, maintains stable material temperatures, and saves energy.

[0041] In terms of waterproofing and hydrophobicity, the directional enrichment of fluorinated segments on the coating surface significantly reduces surface energy, resulting in a water contact angle exceeding 120 degrees. Rainwater and condensation roll off in a spherical pattern, making it difficult to wet the surface. Moisture cannot remain on the coating surface for extended periods, greatly reducing the driving force for water pressure penetration and minimizing the adhesion of dust and contaminants with water flow, thus giving the coating a self-cleaning effect. The highly dense siloxane and isocyanate cross-linked networks formed by moisture curing seal the micropores within the coating and the gaps between filler particles, making it difficult for water molecules to penetrate the coating body. After prolonged immersion in water, the coating does not exhibit blistering, swelling, peeling, or other deterioration phenomena, demonstrating consistently stable moisture resistance and water vapor barrier capabilities.

[0042] In terms of adhesion and durability, the polyurethane-acrylate interpenetrating network provides strong bonding to a variety of substrates, including concrete, steel, and aluminum alloys. The urethane, urea, and carboxyl groups on the polymer segments chemically adsorb hydroxyl groups onto the inorganic substrate surface, while the silanol groups generated after the hydrolysis of the siloxane crosslinking agent directly participate in the condensation reaction with the substrate surface, forming chemical bonds. This dual physical and chemical anchoring results in the coating achieving the highest rating in cross-cut adhesion tests. The coating exhibits a balanced flexibility and hardness, allowing it to adapt to thermal expansion and contraction of the substrate due to temperature changes without cracking or peeling. The chemical inertness of the fluorocarbon segments and the high-strength crosslinking network also endow the coating with excellent weather resistance and chemical resistance, resulting in a long service life under outdoor exposure and in industrial environments.

[0043] In terms of environmental protection and construction, this coating uses water as a dispersion medium and has extremely low volatile organic compound (VOC) content. Its production, transportation, and construction processes have minimal impact on human health and the environment, meeting low VOC emission regulations and allowing for safe use in poorly ventilated spaces. The dual curing mechanism enables the coating to rapidly acquire surface strength and waterproofing after UV irradiation, providing resistance to sudden rainfall shortly after application, reducing waiting time between processes and improving construction efficiency. Its long pot life and rapid surface drying allow for both large-area continuous application and localized repairs. This coating has wide applicability in various applications, including building exteriors, color steel panels, industrial storage tanks, and pipelines. Attached Figure Description

[0044] Figure 1 A flowchart illustrating the preparation method of the fluorocarbon-modified waterborne thermal insulation and waterproof curing coating provided in this embodiment of the invention; Figure 2 This is a comparison chart of thermal conductivity. Figure 3 A comparison chart of water contact angles; Figure 4 This is a comparison chart of adhesion levels; Figure 5 This is a comparison chart of thermal insulation temperature differences; Figure 6 A comparison chart of VOC content; Figure 7 This is a comparison chart of water resistance. Detailed Implementation

[0045] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0046] The accompanying drawings are for illustrative purposes only and are schematic diagrams, not actual images. They should not be construed as limiting the scope of this application. To better illustrate the embodiments of the present invention, some parts in the drawings may be omitted, enlarged, or reduced, and do not represent the actual dimensions of the product. It is understandable to those skilled in the art that some well-known structures and their descriptions may be omitted in the drawings.

[0047] In the accompanying drawings of the embodiments of the present invention, the same or similar reference numerals correspond to the same or similar components. In the description of the present invention, it should be understood that if terms such as "upper," "lower," "left," "right," "inner," and "outer" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, the terms used to describe positional relationships in the drawings are only for illustrative purposes and should not be construed as limiting the present application. For those skilled in the art, the specific meaning of the above terms can be understood according to the specific circumstances.

[0048] In the description of this invention, unless otherwise explicitly specified and limited, the term "connection" or similar designation indicating a connection between components should be interpreted broadly. For example, it can refer to a fixed connection, a detachable connection, or an integral part; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can refer to the internal communication between two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0049] In the following embodiments, unless otherwise specified, the dry film thickness of the coating is controlled between 0.5 and 2.0 mm (single layer) or the total thickness does not exceed 3 mm. The thermal insulation temperature difference test conditions are as follows: a 500W infrared lamp is used to irradiate the coating surface vertically at a distance of 30 cm, the ambient temperature is 25±2℃, the steel plate size is 100mm×100mm×1mm, a thermocouple thermometer is attached to the back, the temperature of the back plate is recorded after irradiation for 30 minutes, and the temperature difference is calculated by comparing it with the uncoated blank steel plate.

[0050] Reference Figures 1-7 This application provides the following embodiments and comparative examples.

[0051] Example 1 This embodiment provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating, which is composed of the following components by weight: 45 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion; 12 parts of hollow glass microspheres; 7 parts of silica aerogel powder; 1.5 parts of ultraviolet photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone; 3 parts of room temperature moisture curing crosslinking agent 3-methacryloyloxypropyltrimethoxysilane; 2.2 parts of additives; and 29.3 parts of deionized water. The additives consist of 0.4 parts of dispersant, 0.3 parts of defoamer, 0.4 parts of leveling agent, 0.3 parts of thickener, 0.1 parts of mildew inhibitor, and 0.7 parts of film-forming aid.

[0052] The preparation of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion is as follows: 100g of polytetrahydrofuran ether diol (NHDD), 6g of dimethylolpropionic acid, and 44.4g of isophorone diisocyanate (NCO:OH molar ratio 1.6) with a number average molecular weight of 2000 were mixed. 0.075g of dibutyltin dilaurate catalyst was added, and the mixture was reacted at 80℃ for 2 hours. Then, 3g of hydroxyethyl methacrylate was added, and the reaction was continued for 1 hour to obtain an isocyanate-terminated polyurethane prepolymer containing olefinic unsaturated double bonds. 12g of perfluorohexylethyl acrylate, 40g of butyl acrylate, and 28g of methyl methacrylate were added to this prepolymer. After stirring evenly, the mixture was neutralized to pH approximately 7.2 with 4.2g of triethylamine. 230g of deionized water was added under high-speed stirring at 2000rpm for emulsification and dispersion to obtain the emulsion. 0.4 g of ammonium persulfate was added to the emulsion, and an emulsion copolymerization reaction was carried out at 80 °C. The reaction time was controlled so that the monomer conversion rate was approximately 85% (determined by gravimetric method). After cooling, the product was discharged to obtain a fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion with a solid content of approximately 40%. The iodine value of the polymer in this emulsion was determined to be 6.2 mgI2 / g, indicating that it contains a sufficient amount of polymerizable double bonds.

[0053] The preparation steps of the coating are as follows: The above copolymer emulsion is mixed with deionized water, dispersant, defoamer, leveling agent, thickener, mildew inhibitor, and film-forming aid. The mixture is stirred at 500 rpm for 20 minutes to obtain a homogeneous slurry. A true density of 0.20 g / cm³ is added to the slurry. 3 Hollow glass microspheres with a particle size D50 of 40 μm and a specific surface area of ​​800 m² 2 / g of silica aerogel powder with an average pore size of 20nm was stirred at 300rpm for 40 minutes until the filler was uniformly dispersed. Finally, a UV initiator and a room temperature moisture curing crosslinking agent were added, and the mixture was stirred at 200rpm for 10 minutes to obtain the coating.

[0054] Coating curing method: Apply the coating to the substrate surface by scraping or spraying, controlling the dry film thickness to approximately 1.0 mm. First, irradiate with 365 nm ultraviolet light at an energy of 1200 mJ / cm². 2 This process allows the coating surface to cure into a film; subsequently, it is left to stand for 7 days in an environment with a temperature of 25°C and a relative humidity of 60%, and deep cross-linking is completed through the alkoxysilane hydrolysis and condensation initiated by moisture.

[0055] The working principle and effect of the coating in this embodiment: The perfluorohexyl ethyl segments in the fluorocarbon modified polymer are oriented towards the surface during film formation, giving the coating hydrophobic and self-cleaning properties; the hollow glass microspheres and aerogel powder synergistically form a hierarchical porous structure, effectively blocking heat conduction; ultraviolet light initiation promotes rapid cross-linking of surface double bonds to form a dense surface layer, while moisture curing deeply cross-links alkoxysilanes and enhances their chemical bonding with the substrate. The resulting coating surface is smooth and flat, with a measured thermal conductivity of 0.042 W / (m·K), a water contact angle of 126°, and a cross-cut adhesion rating of 0. After immersion in water for 7 days, the coating showed no blistering or peeling. When applied to a 1 mm thick steel plate, the back plate temperature was 18°C ​​lower than that of the blank steel plate after 30 minutes of infrared lamp irradiation. The pot life was tested to be 5.5 hours, and the surface drying time was 35 minutes.

[0056] Example 2 This embodiment provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating, which is composed of the following components by weight: 55 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion; 8 parts of hollow glass microspheres; 10 parts of silica aerogel powder; 1 part of ultraviolet photoinitiator 1-hydroxycyclohexylphenyl ketone; 5 parts of room temperature moisture curing crosslinking agent dimethylpyrazole-blocked hexamethylene diisocyanate trimer; 3 parts of additives; and 18 parts of deionized water. The additives consist of 0.5 parts of dispersant, 0.3 parts of defoamer, 0.6 parts of leveling agent, 0.4 parts of thickener, 0.2 parts of mildew inhibitor, and 1.0 part of film-forming aid.

[0057] Preparation of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion: 100g of polybutylene adipate diol (number average molecular weight 2000), 7g of dimethylolbutyric acid (DMOH), and 38g of hexamethylene diisocyanate were mixed with an NCO to OH molar ratio of 1.8. 0.08g of dibutyltin dilaurate was added, and the mixture was reacted at 75℃ for 2.5 hours. Then, 4g of hydroxyethyl acrylate was added, and the reaction continued for 0.8 hours to obtain a polyurethane prepolymer containing unsaturated double bonds. 18g of perfluorohexylethyl acrylate, 45g of butyl acrylate, and 22g of methyl methacrylate were added to the prepolymer. After thorough mixing, the pH was adjusted to 7.0 with ammonia. 220g of deionized water was added under high-speed shear at 2500 rpm to emulsify, yielding an emulsion. 0.5g of potassium persulfate was added to the emulsion, and an emulsion copolymerization reaction was carried out at 85℃, controlling the conversion rate at 88%, to obtain a fluorocarbon-modified copolymer emulsion with a solid content of approximately 42%. Iodine value: 7.1 mgI2 / g.

[0058] Coating preparation: Mix the emulsion with deionized water and all additives, and stir at 600 rpm for 15 minutes; add a true density of 0.30 g / cm³. 3 Hollow glass microspheres with a particle size D50 of 60 μm and a specific surface area of ​​600 m² 2 / g of silica aerogel powder with an average pore size of 35nm was stirred at 250rpm for 50 minutes; then a UV photoinitiator and a blocking crosslinking agent were added, and the mixture was stirred at 150rpm for 10 minutes before being discharged.

[0059] Curing method: After coating application, with a dry film thickness of 1.2mm, heat at 100℃ for 15 minutes to de-encapsulate the blocked isocyanate and release the active isocyanate groups; then irradiate with 365nm ultraviolet light at an energy of 800mJ / cm². 2 Surface curing is performed; finally, it is cured for 5 days in an environment with a temperature of 30℃ and a relative humidity of 75% to complete moisture crosslinking.

[0060] This embodiment achieves a higher cross-linking density in the coating through a triple synergistic process of closed isocyanate thermal desealing, photocuring, and moisture curing. The measured thermal conductivity is 0.038 W / (m·K), the water contact angle is 132°, the adhesion is grade 0, and it exhibits no abnormalities after 7 days of water resistance. Under infrared light irradiation, the temperature difference on the back panel reaches 21°C. Furthermore, the coating demonstrates good flexibility, remaining uncrackled when bent or folded. The pot life is 4.8 hours, and the surface drying time is 25 minutes.

[0061] Example 3 This embodiment provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating, which is composed of the following components by weight: 38 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion; 18 parts of hollow glass microspheres; 5 parts of silica aerogel powder; 2 parts of ultraviolet photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 5 parts of room temperature moisture curing crosslinking agent composition, which is compounded from 3-methacryloyloxypropyltrimethoxysilane and hexamethylene diisocyanate trimer blocked by dimethylpyrazole at a weight ratio of 1:1.5; 4 parts of additives; and 28 parts of deionized water. The additives consist of 0.8 parts of dispersant, 0.5 parts of defoamer, 0.8 parts of leveling agent, 0.5 parts of thickener, 0.2 parts of mildew inhibitor, and 1.2 parts of film-forming aid.

[0062] Preparation of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion: 100g of polypropylene glycol, 5g of dimethylolpropionic acid, and 30g of toluene diisocyanate were mixed at a molar ratio of NCO to OH of 1.5. 0.05g of dibutyltin dilaurate was added, and the mixture was reacted at 70℃ for 3 hours. Then, 3.5g of hydroxyethyl methacrylate was added, and the reaction was continued for 0.5 hours to obtain a prepolymer containing double bonds. 15g of perfluorobutyl ethyl acrylate, 38g of butyl acrylate, and 27g of methyl methacrylate were added and stirred evenly. The mixture was neutralized with 3.5g of triethylamine, and 210g of deionized water was added at 3000rpm for emulsification. 0.3g of ammonium persulfate was added to the emulsion, and the emulsion copolymerization reaction was carried out at 75℃. After the conversion rate reached 92%, 1.5g of trimethylolpropane triacrylate was added, and the reaction was continued for 20 minutes to obtain a copolymer emulsion with a solid content of approximately 38%. Iodine value: 5.8 mgI2 / g.

[0063] Coating preparation: Mix the emulsion, deionized water, and additives at 400 rpm for 25 minutes; add a true density of 0.40 g / cm³. 3 Hollow glass microspheres with a particle size D50 of 25 μm and a specific surface area of ​​950 m² 2 / g of silica aerogel powder with an average pore size of 8nm was stirred at 350rpm for 30 minutes; finally, a UV photoinitiator and a mixed crosslinking agent were added, and the mixture was stirred at 100rpm for 15 minutes.

[0064] Curing method: Dry film thickness 1.5mm, first heat at 90℃ for 20 minutes to unblock the isocyanate, then use ultraviolet light with a wavelength of 365nm and an energy of 1500mJ / cm². 2 Irradiation followed by moisture curing at 20°C and 50% relative humidity for 7 days.

[0065] The resulting coating has a thermal conductivity of 0.045 W / (m·K), a water contact angle of 128°, an adhesion rating of 0, and remains intact after 7 days of water resistance. Its infrared back temperature is 19°C lower than that of the blank steel plate. Due to the synergistic crosslinking of silane and isocyanate, the coating possesses both high hardness and elasticity, exhibiting excellent impact resistance.

[0066] Example 4 This embodiment provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating, which is composed of the following components by weight: 30 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion; 5 parts of hollow glass microspheres; 3 parts of silica aerogel powder; 0.5 parts of ultraviolet photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone; 1 part of room temperature moisture curing crosslinking agent 3-methacryloyloxypropyltrimethoxysilane; 1 part of additives; and 35 parts of deionized water. The additives consist of 0.1 parts of dispersant, 0.1 parts of defoamer, 0.1 parts of leveling agent, 0.1 parts of thickener, 0.05 parts of mildew inhibitor, and 0.55 parts of film-forming aid.

[0067] Preparation of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion: 100g of polytetrahydrofuran ether diol (NHDD), 2g of dimethylolpropionic acid, and 26.6g of isophorone diisocyanate (NCO:OH molar ratio 1.2) were mixed. 0.006g of dibutyltin dilaurate catalyst was added, and the mixture was reacted at 60℃ for 3 hours. Then, 1g of hydroxyethyl methacrylate was added, and the reaction was continued for 0.5 hours to obtain an isocyanate-terminated polyurethane prepolymer containing olefinic unsaturated double bonds. 5g of perfluorobutyl ethyl acrylate, 50g of butyl acrylate, and 45g of methyl methacrylate were added to the prepolymer. After stirring evenly, the mixture was neutralized to pH approximately 6.5 with 1.4g of triethylamine. 200g of deionized water was added under high-speed stirring at 1000rpm for emulsification and dispersion to obtain the emulsion. Add 0.12 g of ammonium persulfate (0.12% of the total monomer weight) to the emulsion, and carry out emulsion copolymerization at 70 °C. Control the conversion rate to 75% (a lower conversion rate to retain more double bonds). Cool and discharge to obtain a fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion with a solid content of approximately 35%. Iodine value: 8.3 mgI2 / g.

[0068] Preparation of the coating: The above copolymer emulsion was mixed with deionized water, dispersant, defoamer, leveling agent, thickener, mildew inhibitor, and film-forming aid. The mixture was stirred at 300 rpm for 30 minutes to obtain a homogeneous slurry. A true density of 0.45 g / cm³ was added to the slurry. 3 Hollow glass microspheres with a particle size D50 of 80 μm and a specific surface area of ​​500 m² 2 / g of silica aerogel powder with an average pore size of 50nm was stirred at 200rpm for 60 minutes until the filler was uniformly dispersed; finally, a UV photoinitiator and a room temperature moisture curing crosslinking agent were added, and the mixture was stirred at 100rpm for 15 minutes to obtain the coating.

[0069] Curing method: The coating is applied to the substrate surface with a dry film thickness of 0.6 mm, and then irradiated with ultraviolet light at a wavelength of 320 nm and an irradiation energy of 500 mJ / cm². 2 This process allows the coating surface to cure into a film; subsequently, it is left to stand for 7 days in an environment with a temperature of 5°C and a relative humidity of 30%, and deep cross-linking is completed through the alkoxysilane hydrolysis and condensation initiated by moisture.

[0070] In this embodiment, the amounts of each component are at a low level. Due to the low amount of emulsion, the amount of resin solids acting as film-forming substances in the system is correspondingly reduced, resulting in lower viscosity of the coating and easier spraying. The low amount of filler makes the coating surface more delicate and smooth, suitable for thin-layer coating applications where high appearance requirements are required. Although the amounts of UV photoinitiator and moisture-curing crosslinking agent are low, under the irradiation energy and curing conditions, photocuring can still trigger surface double bond crosslinking to form an initial skin layer. The alkoxysilane slowly hydrolyzes and condenses under low humidity, ultimately achieving internal and external crosslinking of the coating.

[0071] The measured thermal conductivity of the coating is 0.058 W / (m·K), the water contact angle is 122°, the cross-cut adhesion is grade 0, and the coating showed no blistering or peeling after immersion in water for 7 days. After 30 minutes of infrared lamp irradiation, the back panel temperature was 12°C lower than the blank steel plate. The pot life is 7.2 hours, and the surface drying time is 52 minutes.

[0072] Example 4 exhibits the lowest VOC content (12 g / L), approaching zero VOC levels, making it particularly suitable for indoor use, schools, hospitals, and other locations with extremely high air quality requirements. Although Example 5 uses higher amounts of each component, through optimized emulsion synthesis processes and vacuum removal technology, the VOC content is still controlled below 38 g / L, fully meeting environmental protection requirements. The VOC content of all examples is significantly lower than that of traditional solvent-based heat-insulating coatings (typically >300 g / L), and there is no irritating odor during application and curing, making them environmentally friendly and beneficial to human health.

[0073] Example 5 This embodiment provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating, which is composed of the following components by weight: 60 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion; 20 parts of hollow glass microspheres; 12 parts of silica aerogel powder; 3 parts of ultraviolet photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 6 parts of room temperature moisture curing crosslinking agent composition, which is compounded by 3-methacryloyloxypropyltrimethoxysilane and hexamethylene diisocyanate trimer blocked by dimethylpyrazole in a weight ratio of 1:3; 5 parts of additives; and 10 parts of deionized water. The additives consist of 1.0 part of dispersant, 0.5 part of defoamer, 0.8 part of leveling agent, 0.5 part of thickener, 0.2 part of mildew inhibitor, and 2.0 part of film-forming aid.

[0074] Preparation of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion: 100g of polybutylene adipate diol (number average molecular weight 2000), 8g of dimethylolbutyric acid (DMOH), and 50.5g of toluene diisocyanate were mixed with an NCO to OH molar ratio of 2.0. 0.3g of dibutyltin dilaurate catalyst was added, and the mixture was reacted at 85℃ for 1.5 hours. Then, 5g of hydroxyethyl acrylate was added, and the reaction was continued for 1 hour to obtain an isocyanate-terminated polyurethane prepolymer containing olefinic unsaturated double bonds. 30g of perfluorohexylethyl acrylate, 35g of butyl acrylate, and 35g of methyl methacrylate were added to this prepolymer. After stirring evenly, the mixture was neutralized to pH approximately 7.5 with 5.5g of ammonia. 240g of deionized water was added under high-speed stirring at 3000rpm for emulsification and dispersion to obtain the emulsion. Add 0.7g of potassium persulfate to the emulsion and carry out emulsion copolymerization at 90℃. Control the conversion rate at 82%, cool and discharge to obtain a fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion with a solid content of approximately 45%. Iodine value: 6.9 mgI2 / g.

[0075] Preparation of the coating: The above copolymer emulsion was mixed with deionized water, dispersant, defoamer, leveling agent, thickener, mildew inhibitor, and film-forming aid, and stirred at 800 rpm for 10 minutes to obtain a homogeneous slurry; a true density of 0.12 g / cm³ was added to the slurry. 3 Hollow glass microspheres with a particle size D50 of 10 μm and a specific surface area of ​​1000 m² 2 / g of silica aerogel powder with an average pore size of 5nm was stirred at 500rpm for 20 minutes until the filler was uniformly dispersed; finally, a UV photoinitiator and a room temperature moisture curing crosslinking agent were added, and the mixture was stirred at 300rpm for 5 minutes to obtain the coating.

[0076] Curing method: After coating application, with a dry film thickness of 2.0 mm, first heat at 120℃ for 5 minutes to de-encapsulate the blocked isocyanate; then irradiate with 400 nm ultraviolet light at an energy of 2000 mJ / cm². 2 Surface curing is performed; finally, it is cured for 7 days in an environment with a temperature of 40℃ and a relative humidity of 90% to complete moisture crosslinking.

[0077] In this embodiment, the dosage of each component is at a high level. The high emulsion dosage provides ample film-forming material for the coating, resulting in excellent mechanical properties. The high filler dosage makes the internal cavities and nanopores of the coating dense, significantly enhancing the thermal insulation effect. The high crosslinking agent dosage, combined with the thermal deblocking of the blocked isocyanate, forms a dense organic-inorganic hybrid crosslinking network, greatly improving the coating's density and water resistance. The high film-forming aid dosage ensures that the emulsion particles can still fully fuse and form a film in low-water-content formulations.

[0078] The measured thermal conductivity of the coating is 0.031 W / (m·K), the water contact angle is 135°, the cross-cut adhesion is grade 0, and after immersion in water for 7 days, the coating showed no blistering or peeling. After 30 minutes of infrared lamp irradiation, the back panel temperature was 24°C lower than the blank steel plate. The coating achieved a pencil hardness of 3H, and its impact resistance passed the 50 cm·kg forward and reverse impact tests. The pot life is 2.5 hours, and the surface drying time is 18 minutes.

[0079] Example 6 This embodiment provides a fluorocarbon-modified waterborne thermal insulation and waterproof curing coating with hydrophobic filler surface modification, which is composed of the following components by weight: 45 parts of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion; 12 parts of surface-modified hollow glass microspheres; 7 parts of surface-modified silica aerogel powder; 1.5 parts of ultraviolet photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone; 3 parts of room temperature moisture curing crosslinking agent 3-methacryloyloxypropyltrimethoxysilane; 2.2 parts of additives; and 29.3 parts of deionized water. The composition of the additives is the same as in Example 1.

[0080] The steps for modifying the filler surface are as follows: (1) Modification of hollow glass microspheres: The true density of 0.20 g / cm³ was modified. 3 100g of hollow glass microspheres with a particle size D50 of 40μm were added to a high-speed mixer and preheated at 100℃ and 1500rpm for 30 minutes. Then, 2g of hexamethyldisilazane was slowly added dropwise and the reaction was continued to be stirred for 1 hour. After discharge, the material was dried at 120℃ for 2 hours to obtain surface hydrophobic modified hollow glass microspheres.

[0081] (2) Modification of silica aerogel powder: Silica aerogel powder with a specific surface area of ​​800 m² 2 100g of silica aerogel powder with an average pore size of 20nm was dispersed in 1000mL of anhydrous ethanol, and 3g of methyltrimethoxysilane was added. The mixture was ultrasonically dispersed at 60℃ for 2 hours. After filtration, the powder was washed three times with anhydrous ethanol and vacuum dried at 80℃ for 12 hours to obtain surface-hydrophobic modified silica aerogel powder.

[0082] The preparation steps and curing methods of the fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion, coating, and curing method are the same as in Example 1.

[0083] Performance test results: The resulting coating has a smooth and flat surface, a measured thermal conductivity of 0.039 W / (m·K), a water contact angle of 134°, and a cross-cut adhesion rating of 0. After immersion in water for 14 days, the coating showed no blistering, peeling, or discoloration. When applied to a 1 mm thick steel plate and irradiated with an infrared lamp for 30 minutes, the back plate temperature was 19°C lower than that of the blank steel plate. The pot life was tested to be 5.2 hours, and the surface drying time was 32 minutes. After three months of sealed storage at room temperature, the filler showed no sedimentation or delamination, and the coating performance remained largely unchanged.

[0084] Compared with Example 1 (unmodified filler), this example modifies the surface of the filler with a silane coupling agent to make it hydrophobic, which further improves the interfacial bonding force between the filler and the resin matrix, reduces the water absorption rate of the coating, and significantly improves the water resistance and long-term stability. At the same time, the thermal conductivity is slightly reduced, and the hydrophobic performance is further enhanced.

[0085] Comparative Example 1 Compared with Example 1, the fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion was replaced with a fluorine-free ordinary waterborne polyurethane-acrylate emulsion. No fluorinated acrylate monomers were used in the preparation of this emulsion, and the remaining components and preparation methods were the same as in Example 1.

[0086] The resulting coating had a thermal conductivity of 0.044 W / (m·K) and a water contact angle of only 85°. After immersion in water for 24 hours, the contact angle further decreased to 72°, and wetting occurred on the coating surface. The back temperature under infrared lamp irradiation was 14°C lower than that of the blank steel plate. This comparative example shows that the lack of fluorocarbon modification significantly reduced the hydrophobicity of the coating, resulting in poorer waterproofing and self-cleaning functions.

[0087] Comparative Example 2 Compared with Example 1, 12 parts of hollow glass microspheres and 7 parts of silica aerogel powder were replaced with an equal weight of heavy calcium carbonate filler, while the rest remained unchanged.

[0088] The thermal conductivity of the coating increased to 0.18 W / (m·K), resulting in a significant deterioration in thermal insulation performance. The back temperature under infrared lamp irradiation was only 4°C lower than that of the blank steel plate. This comparative example illustrates that the insulating combination of hollow glass microspheres and aerogel powder is key to achieving low thermal conductivity.

[0089] Comparative Example 3 Compared with Example 1, the coating components are the same, but the curing method is only ultraviolet irradiation curing, without subsequent room temperature humidity curing, that is, the coating is tested immediately after ultraviolet irradiation.

[0090] The coating surface was cured but the internal cross-linking was insufficient, with a thermal conductivity of 0.049 W / (m·K), a water contact angle of 115°, and an adhesion rating of 2. After 24 hours of water immersion, blistering occurred at the coating edges. In contrast, Example 1, which underwent 7 days of moisture curing, showed an adhesion rating of 0. This comparative example demonstrates that simple UV curing is insufficient for deep cross-linking of thick coatings, and post-moisture curing is crucial for improving adhesion, water resistance, and overall performance.

[0091] Experimental Data Summary Table

[0092] As can be seen from the above embodiments and comparative examples, the fluorocarbon modified water-based thermal insulation and waterproof curing coating provided in this application achieves excellent results in terms of thermal insulation, waterproof durability and ease of construction through the synergistic mechanism of fluorocarbon hydrophobicity, dual-level filler thermal insulation and light-moisture dual curing, and has made significant progress.

[0093] Among them, the effective thermal conductivity of the coating after curing The following structure-heat transfer coupling equations must be satisfied: ;in: Thermal conductivity of the dried and cured matrix of fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion, in units of ; , These represent the effective volume fractions of hollow glass microspheres and silica aerogel powder in the coated dry film, respectively, and are dimensionless. ; The fluorocarbon interface coupling coefficient has a range of values. ; The fluorine-carbon segment surface enrichment factor is dimensionless, and is the ratio of fluorine surface concentration to bulk concentration measured by XPS, within a certain range. ; The apparent activation energy of the moisture crosslinking reaction is given in units of 1000 kJ / m². Measured by DSC method, range ; Let be the ideal gas constant. ; This is the room temperature moisture curing temperature, in units of ,generally ; , These are the true density of hollow glass microspheres and the bulk density of silica aerogel powder, respectively, in units of... ; The porosity coordination coefficient has a range of values. ; For reference density, a fixed value .

[0094] Example: Taking Example 2 as an example Known conditions in Example 2: (Measured thermal conductivity of pure matrix); , (Volume fraction); (Fitting constants); (XPS test results); , ; ; , (Aerogel bulk density); , .

[0095] Calculation steps ; ; ; Index Term ; ; ; ; ; ; denominator ; merge: ; Step by step: ; ; ; ; Compared with measured values Comparison: Predicted values Actual measurement The relative error is approximately Explain the parameters. , The formula needs to be fine-tuned, for example, by taking... , available .

[0096] In practical applications, each manufacturer can calibrate a set of parameters based on its own standard formula to achieve accurate prediction.

[0097] Further parameter descriptions:

[0098] Technical effects: The required thermal conductivity can be calculated by back-calculating the target thermal conductivity. , or minimum This reduces the need for trial and error experiments.

[0099] Through the index term It can be assessed whether the current curing temperature is sufficient. If the thermal conductivity is too high, the curing temperature can be lowered or a high activation energy crosslinking agent can be selected to increase the remaining crosslinking driving force, increase interfacial defects, and increase interfacial thermal resistance, thereby reducing the thermal conductivity.

[0100] Density ratio This indicates that when The smaller (lightweight microbeads) and The smaller the aerogel (lighter), the stronger the synergistic effect and the lower the thermal conductivity of the coating. It is recommended to use high-porosity lightweight microspheres and ultra-low-density aerogels in combination.

[0101] Working principle and process: First, calculate the filler volume fraction based on the coating formulation. , and density , ; The fluorine concentration ratio on the coating surface to the bulk phase was obtained by measuring with XPS. ; The apparent activation energy of the moisture crosslinking reaction was measured using differential scanning calorimetry (DSC) at different heating rates. ; Set the actual construction and curing temperature (Kelvin); The above parameters are compared with empirical coefficients , (Substitute the values ​​from a pre-calibrated formula of the same type into the equation;) Output predicted effective thermal conductivity ; If the predicted value is higher than the target value (e.g.) If the aerogel usage is increased, it is recommended to: increase the amount of aerogel used (to improve...). ), reduce maintenance temperature (reduce) Alternatively, choose a high activation energy crosslinking agent (to increase...) ); If the predicted value is lower than the target value, the following can be considered: reduce the amount of microbeads or aerogel, increase the curing temperature, or select a low activation energy crosslinking agent; Repeat the iterations until the insulation requirements are met, and finally determine the formula and construction process parameters.

[0102] This process organically combines coating chemistry, curing kinetics, and heat transfer physics, enabling the rational design of functional coatings and significantly improving R&D efficiency and product performance consistency.

[0103] The working principle of this application is as follows: At the film-forming material level, fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsions are key to coatings. The chemically bonded perfluoroalkyl segments on the polymer molecular chain spontaneously migrate and accumulate at the coating-air interface during drying and curing due to their low surface energy, resulting in stable hydrophobicity on the cured coating surface. Rainwater, upon contact with the coating, rolls off as droplets, making it difficult to spread and wet, and preventing moisture penetration into the coating interior. Simultaneously, during the emulsion polymerization stage, polymerizable double bonds are introduced into the polyurethane segments through hydroxyl-containing olefinic unsaturated monomers. Subsequent copolymerization with acrylate monomers (controlling the conversion rate or adding multifunctional monomers to retain the double bonds) forms an interpenetrating network structure of polyurethane and acrylate molecules, with a sufficient number of unsaturated double bonds remaining on the polymer backbone. This structure combines the flexibility and elasticity of the polyurethane segments with the strength and hardness of the acrylate segments, resulting in coatings with outstanding adhesion and crack resistance. Furthermore, the residual double bonds on the backbone provide crosslinking active sites for subsequent photocuring reactions.

[0104] In terms of thermal insulation fillers, hollow glass microspheres contain closed, rarefied gas cavities, with the solid phase occupying only a tiny proportion of the particle volume. Heat flow along the microsphere walls follows a long path with a small cross-sectional area. Silica aerogel powder, on the other hand, consists of a three-dimensional network formed by the stacking of nano-sized silica particles. Its pore size is much smaller than the mean free path of air molecules, making convective heat transfer difficult within the nanopores. Solid-phase heat conduction is also significantly suppressed due to the extremely limited contact points between particles. The combination of micron-sized hollow glass microspheres and nano-sized aerogel powder in the coating forms a multi-scale porous system, weakening heat transfer from two dimensions: blocking solid-phase conduction and suppressing gas-phase thermal motion, thus contributing to the coating's low thermal conductivity. When the two fillers are combined in an appropriate ratio, the nanoparticles can fill the gaps between the microspheres, increasing the filler stacking density and preventing the large gaps between particles that would result in incomplete blocking of the thermal conduction pathways when using microspheres alone.

[0105] In terms of curing mechanism, the coating employs a sequential process of light curing and moisture curing. After application, the coating is first irradiated with ultraviolet light, causing the initiator to decompose and generate free radicals. This rapidly initiates a cross-linking reaction of the unsaturated double bonds remaining on the polymer molecular chains, forming a dense, solid thin layer on the surface of the coating within seconds to tens of seconds. This skin not only immediately provides the coating with waterproofing and stain / dust resistance but also slows down the rapid evaporation of moisture from within the coating, preserving the necessary moisture environment for subsequent moisture curing. Simultaneously, by controlling the degree of ultraviolet curing (e.g., gradient curing) or selecting appropriate hydrophilic monomers, sufficient water vapor transmission rate (not less than 10 g / (m²)) is ensured on the surface. 2 (24h) This allows moisture to penetrate deep into the coating. Subsequently, the moisture-curing crosslinking agents inside the coating—including compounds containing alkoxysilane groups or blocked polyisocyanates—gradually undergo hydrolysis-condensation or deblocking-addition reactions using air humidity and residual moisture in the coating. The degree of crosslinking gradually increases from the surface inwards, ultimately connecting polymer segments along the entire thickness of the coating into a continuous and dense three-dimensional network. The sequential combination of photo-initiated surface setting and moisture-driven deep crosslinking solves the problems of limited penetration depth and insufficient crosslinking in thick coatings with UV curing alone. It also avoids the shortcomings of simple moisture curing, such as slow surface drying, poor initial water resistance, and the strong constraint of environmental humidity on the application window.

[0106] When using blocked polyisocyanate crosslinking agents, a brief heating process is applied after coating application to remove the blocker from the isocyanate groups, releasing free isocyanates. These active groups react with water to form urea bonds and release carbon dioxide. They also react with active hydrogen atoms such as hydroxyl and amino groups on the polymer chain to form urethane and urea bonds. The dense distribution of crosslinking points and high bond energy further enhance the coating's density and mechanical strength. If the crosslinking agent contains methacryloyloxy silanes, their unsaturated double bonds can participate in UV-induced free radical crosslinking, anchoring silane molecules in the photocurable network. Furthermore, the siloxane crosslinking network generated by the partial hydrolysis and condensation of alkoxysilanes interweaves with the organic crosslinking network formed by isocyanates, achieving organic-inorganic hybrid crosslinking while maintaining both hardness and flexibility.

[0107] How to use: During substrate preparation, remove surface dust, oil, loose layers, and peeling old coatings. Holes and cracks in concrete substrates should be repaired and sanded smooth beforehand; if rust is present on metal substrates, sand until the metal shines through and remove grease with solvent. Unlike most water-based coatings, this coating has good direct adhesion to substrates, eliminating the need for pre-coating with an anti-rust primer when applying to steel or aluminum alloy surfaces, simplifying the process.

[0108] During the paint mixing stage, stir the paint thoroughly after opening the container. If slight separation occurs due to storage, redisperse it using a mixer at low speed. The paint has a long pot life; the prepared paint maintains good coatability for several hours at room temperature. Application methods include spraying, troweling, or roller coating. For large exterior walls and roofs, an airless sprayer is recommended for uniform film formation. For irregular structures such as color steel plates and pipes, roller brushes or trowels can be used. The thickness of a single wet film is determined according to design requirements. Thick coatings should be applied in multiple coats, with each coat spaced between coats until the previous coat is surface dry. The paint surface drying time is relatively short; at room temperature, the surface will be dust-free in about half an hour, allowing for the next coat to be applied or the curing process to begin.

[0109] The curing process has two paths depending on the type of crosslinking agent used. When only a moisture-curing crosslinking agent containing alkoxysilane groups is used, the coating can be naturally cured after UV irradiation. The UV wavelength range is between 320 and 400 nanometers. Common UV light sources such as high-pressure mercury lamps or LED UV curing lamps can be used. The irradiation energy is adjusted according to the coating thickness to ensure complete surface curing without stickiness. After irradiation, the coating is left to stand in a normal temperature and humidity environment. Moisture curing reaction can occur in an environment with a relative humidity range of 30% to 90%, and the temperature can range from 5°C to 40°C. After several days of curing, the deep crosslinking of the coating is completed.

[0110] When using a blocked waterborne polyisocyanate crosslinking agent, an additional heating and desealing step is added before ultraviolet irradiation. The coated substrate is placed in an oven or irradiated with an infrared heater at a temperature controlled between 80 and 120 degrees Celsius for 5 to 30 minutes to remove the sealant and release the active isocyanate groups. After desealing, the aforementioned ultraviolet irradiation and moisture curing steps are immediately followed. The final performance of this coating under normal building conditions tends to stabilize after seven days of curing.

[0111] The above are merely preferred embodiments of the present invention and are not intended to limit the implementation methods and protection scope of the present invention. Those skilled in the art should recognize that any equivalent substitutions and obvious changes made based on the description and illustrations of the present invention should be included within the protection scope of the present invention.

Claims

1. A fluorocarbon-modified water-based thermal insulation waterproofing curing paint, characterized by, By weight, the coating comprises 30-60 parts of fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion, 5-20 parts of hollow glass microspheres, 3-12 parts of silica aerogel powder, 0.5-3 parts of ultraviolet photoinitiator, 1-6 parts of room temperature moisture curing crosslinking agent, 1-5 parts of additives, and 10-35 parts of deionized water. The fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion is prepared by emulsion copolymerization of fluorinated acrylate monomers and polyurethane prepolymers. The fluorinated acrylate monomers are acrylate monomers containing at least one of perfluorohexyl or perfluorobutyl, and the copolymer emulsion contains olefinic unsaturated double bonds that can be polymerized by free radicals. The residual amount of olefinic unsaturated double bonds in the copolymer emulsion is ensured by controlling the copolymerization conversion rate to 70-90% or by adding polyfunctional acrylate monomers after copolymerization, so that its iodine value is not less than 5 mgI2 / g polymer.

2. The fluorocarbon-modified water-based thermal insulation waterproof curing paint according to claim 1, characterized in that, The preparation of the fluorocarbon-modified waterborne polyurethane-acrylate copolymer emulsion includes the following steps: S1: Polyether diol or polyester diol, hydrophilic chain extender, and diisocyanate are mixed at an NCO / OH molar ratio of 1.2–2.0:1 and reacted at 60–85°C for 1.5–3 h in the presence of dibutyltin dilaurate catalyst; then, a hydroxyl-containing olefinic unsaturated monomer is added, and the reaction is continued for 0.5–1 h to obtain an isocyanate-terminated polyurethane prepolymer containing olefinic unsaturated double bonds; wherein the diisocyanate is selected from hexamethylene diisocyanate, isophorone diisocyanate, and toluene diisocyanate. The product contains at least one isocyanate; the hydrophilic chain extender is selected from at least one of dimethylolpropionic acid and dimethylolbutyric acid, and its amount is 2-8% of the weight of polyether diol or polyester diol; the hydroxyl-containing olefinic unsaturated monomer is selected from at least one of hydroxyethyl methacrylate and hydroxyethyl acrylate, and its amount is 1-5% of the weight of polyether diol or polyester diol; the amount of the catalyst is 0.01-0.5% of the total weight of polyether diol or polyester diol, hydrophilic chain extender and diisocyanate. S2: Add fluorinated acrylate monomers and acrylate hard and soft segment monomers to the polyurethane prepolymer. The amount of fluorinated acrylate monomers is 5-30% of the total weight of the fluorinated acrylate monomers and acrylate hard and soft segment monomers, and the amount of acrylate hard and soft segment monomers is 70-95% of the total weight of the fluorinated acrylate monomers and acrylate hard and soft segment monomers. The acrylate hard and soft segment monomers are selected from at least one of butyl acrylate and methyl methacrylate. Stir until homogeneous. Add a neutralizing agent to adjust the pH to 6.5-7.

5. The neutralizing agent is selected from at least one of triethylamine and ammonia water, and its amount is 0.9-1.1 times the molar amount of the hydrophilic chain extender. Deionized water was added under high-speed stirring at 000-3000 rpm for emulsification and dispersion to obtain an emulsion. Subsequently, a water-soluble initiator was added to the emulsion, and an emulsion copolymerization reaction was carried out at 70-90°C. The reaction time was controlled so that the total monomer conversion rate was 70-90%, or after the conversion rate reached more than 90%, 0.5-2% of the total weight of the monomers of multifunctional acrylate monomers was added and the reaction was continued for 10-30 minutes to obtain the fluorocarbon modified waterborne polyurethane-acrylate copolymer emulsion. The water-soluble initiator was selected from at least one of ammonium persulfate and potassium persulfate, and its amount was 0.1-1.0% of the total weight of the fluorinated acrylate monomers and the acrylate soft and hard segment monomers.

3. The fluorocarbon-modified water-based thermal insulation waterproof curing paint according to claim 1, characterized in that, The hollow glass microbead has a true density of 0.12-0.45 g / cm 3 , a particle size D50 of 10-80 mu m, and a thermal conductivity of 0.03-0.08 W / (m*K); the silica aerogel powder has a specific surface area of 500-1000 m 2 / g and an average pore size of 5-50 nm.

4. The fluorocarbon-modified water-based thermal insulation waterproof curing paint according to claim 1, characterized in that, The ultraviolet photoinitiator is selected from one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide; the room temperature moisture-curing crosslinking agent is a compound containing an alkoxysilyl group or a blocked aqueous polyisocyanate, wherein the unblocking temperature of the blocked aqueous polyisocyanate is 80-120°C, and it is selected from one or more of dimethylpyrazole-blocked hexamethylene diisocyanate trimer and diethyl malonate-blocked isophorone diisocyanate trimer; the compound containing an alkoxysilyl group is selected from one or more of 3-methacryloyloxypropyltrimethoxysilane and 3-glycidyl etheroxypropyltrimethoxysilane.

5. The fluorocarbon-modified water-based thermal insulation and waterproof curing coating according to claim 1, characterized in that, The additives comprise the following sub-components in parts by weight of the total coating: 0.1 to 1.0 parts dispersant, 0.1 to 0.5 parts defoamer, 0.1 to 0.8 parts leveling agent, 0.1 to 0.5 parts thickener, 0.05 to 0.2 parts mildew inhibitor, and 0.5 to 2.0 parts film-forming aid.

6. The fluorocarbon-modified water-based thermal insulation and waterproof curing coating according to claim 1, characterized in that, The coating undergoes a dual curing process, comprising: when the room temperature moisture curing crosslinking agent is a blocked waterborne polyisocyanate, firstly, deblocking is performed by heating at 80–120°C for 5–30 minutes; then, ultraviolet radiation curing is performed, with an ultraviolet wavelength of 320–400 nm and an irradiation energy of 500–2000 mJ / cm². 2 This process forms a dense, waterproof layer on the coating surface. Finally, room temperature moisture curing is performed. Under conditions of 30%–90% humidity and 5–40°C, deep cross-linking curing of the coating is achieved through the reaction of the room temperature moisture curing cross-linking agent with moisture. When the room temperature moisture curing cross-linking agent is a compound containing alkoxysilane groups, ultraviolet radiation curing and subsequent room temperature moisture curing are performed directly. Furthermore, after ultraviolet curing, the water vapor transmittance of the coating is not less than 10 g / (m²). 2 • 24h), or gradient curing: first at 300-500 mJ / cm 2 Low-energy ultraviolet irradiation semi-cures the coating. After the coating has basically cured at room temperature and humidity, it is then subjected to 1000-2000 mJ / cm² irradiation. 2 The final surface densification is achieved using high-energy ultraviolet light.

7. The fluorocarbon-modified water-based thermal insulation and waterproof curing coating according to claim 1, characterized in that, The room temperature moisture curing crosslinking agent is a combination of 3-methacryloyloxypropyltrimethoxysilane and dimethylpyrazole-blocked hexamethylene diisocyanate trimer, with a weight ratio of 1:0.3 to 1:

3.

8. The fluorocarbon-modified water-based thermal insulation and waterproof curing coating according to claim 1, characterized in that, The hollow glass microspheres and / or silica aerogel powder are subjected to surface hydrophobic modification treatment with a silane coupling agent, wherein the silane coupling agent is selected from one or more of hexamethyldisilazane, methyltrimethoxysilane, and dimethyldimethoxysilane.

9. The fluorocarbon-modified waterborne thermal insulation and waterproof curing coating according to any one of claims 1 to 6, characterized in that, The volatile organic compound content of the coating is 0-50 g / L.

10. The application of the fluorocarbon-modified waterborne thermal insulation and waterproof curing coating according to any one of claims 1 to 6 on the surface of a metal substrate, characterized in that, The metal substrate is steel or aluminum alloy, and the coating is applied directly to the surface of the metal substrate without the need for pre-coating with a primer.

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