Aging-resistant waterproof building coating and preparation method and application thereof

Abstract

The application relates to the technical field of waterproof coating, and particularly discloses an anti-aging waterproof building coating, a preparation method and application thereof. The anti-aging waterproof building coating comprises fluorocarbon core-shell emulsion, slow-release anti-aging microspheres, ultraviolet shielding fillers, film-forming aids, defoaming agents, thixotropic lubricants and water. The anti-aging waterproof building coating provided by the application has excellent ultraviolet aging resistance, waterproof performance, bonding strength and storage stability after curing, solves the problems that small molecule anti-aging agents in traditional exposed waterproof coatings are prone to migration and loss, and long-term waterproof function of a coating film is quickly attenuated, and makes the cured coating adapt to outdoor waterproof working conditions such as exposed roofs, outer walls, bridges and balconies, and meet the comprehensive requirements of building engineering on long service life protection and low maintenance cost.

Description

Technical Field

[0001] This invention relates to the field of waterproof coating technology, specifically disclosing an aging-resistant waterproof building coating, its preparation method, and its application. Background Technology

[0002] In the field of building waterproofing engineering, exposed waterproof coatings are the core basic material for ensuring the durability of outdoor building structures. They are widely used in exposed roofs, exterior walls, bridges, balconies, and terraces—situations directly exposed to the atmospheric environment. Their core purpose is to form a continuous and dense waterproof membrane through the coating and curing process. This membrane can prevent rainwater, snowmelt, and moisture from penetrating the concrete substrate for a long time, preventing steel corrosion, concrete carbonation, and freeze-thaw damage caused by water erosion. It also withstands the continuous effects of natural aging factors such as ultraviolet radiation, diurnal temperature variations, and acid / alkaline rainwater erosion, meeting the needs of outdoor buildings for long-term protection and low maintenance costs.

[0003] To slow down the aging process of exposed waterproof coatings in outdoor environments, existing technologies often employ the addition of small-molecule UV absorbers and hindered amine light stabilizers to the coating. The UV absorbers absorb harmful UV light and convert it into harmlessly dissipated heat, while the hindered amine light stabilizers capture free radicals and block the oxidative degradation chain reaction of polymer molecules. The synergistic effect of these two agents extends the service life of the coating to a certain extent. However, the external addition method has significant shortcomings: small-molecule UV absorbers and light stabilizers are physically dispersed in the coating film and have no chemical bonds with the polymer matrix. Under long-term rain erosion, alternating hot and cold temperatures, and wet-dry cycles, small-molecule additives easily migrate from the interior of the coating film to the surface and are washed away with rainwater, resulting in a decrease in protective effect over time and accelerated aging of the coating film in the later stages. UV absorbers have saturated absorption characteristics. When the UV absorbers on the surface of the coating film are reduced due to migration, decomposition, or consumption, excess UV light can penetrate to the deep layers of the coating film, causing photo-oxidative degradation of the polymer matrix, resulting in aging damage from the surface inward. Some UV absorbers themselves will undergo photochemical decomposition reactions under long-term UV irradiation. The decomposition products not only lose their absorption function but may also accelerate the discoloration and embrittlement of the surrounding polymer matrix. In addition, traditional exposed waterproof coatings mostly use ordinary acrylic emulsions as film-forming substances. The C-C bonds and ester groups in their molecular backbone are sensitive to UV light and lack intrinsic aging resistance. After several years of outdoor exposure, problems such as chalking, cracking, and loss of waterproof function will appear.

[0004] To address the aforementioned technical shortcomings, there is an urgent need to improve existing technologies. Summary of the Invention

[0005] To address the problems of poor UV aging resistance, easy migration and loss of small-molecule antioxidants, and rapid degradation of the waterproof function of coatings in the long term in existing exposed waterproof coatings, this invention provides an anti-aging waterproof building coating, its preparation method, and its application. The anti-aging waterproof building coating comprises a fluorocarbon core-shell emulsion, slow-release antioxidant microspheres, UV-shielding filler, film-forming aid, defoamer, thixotropic lubricant, and water. The anti-aging waterproof building coating provided by this invention, through the synergistic effect of its components, constructs a multi-level anti-aging protection system from three dimensions: polymer bulk weather resistance, long-term slow-release of antioxidants, and inorganic UV physical shielding. This improves the UV aging resistance, waterproof performance, and long-term reliability of the coating film, avoiding the problem of single and unsustainable anti-aging performance in traditional coatings, extending the outdoor service life of the coating film, and meeting the protection needs of exposed roofs, exterior walls, bridges, balconies, and other outdoor waterproofing conditions subjected to long-term sun and rain exposure. Meanwhile, the aging-resistant and waterproof building coating provided by this invention is a single-component system that can be used immediately after opening the can without the need for on-site metering and mixing. It is easy to operate, has no applicable period limit, and has good storage stability, meeting the requirements of environmentally friendly building functional coatings.

[0006] The present invention provides an aging-resistant and waterproof building coating, which, by weight, comprises the following components: 40-55 parts of fluorocarbon core-shell emulsion, 15-30 parts of slow-release anti-aging microspheres, 5-10 parts of UV-shielding filler, 2-5 parts of film-forming aid, 0.1-0.5 parts of defoamer, 0.1-0.5 parts of thixotropic lubricant, and 5-15 parts of water.

[0007] In this invention, the fluorocarbon core-shell emulsion serves as the core film-forming material. The shell layer is copolymerized from trifluoroethyl methacrylate and methyl methacrylate. The CF bond energy in the trifluoroethyl methacrylate molecule is as high as 485 kJ / mol, far exceeding the 348 kJ / mol of the C-C bond. Ultraviolet photons are insufficient to directly break the CF bond, thus endowing the shell layer with excellent resistance to UV oxidative degradation. Simultaneously, the low surface energy of fluorine atoms gives the shell layer a hydrophobic self-cleaning function. Rainwater beads off the coating surface, reducing the water film's residence time and decreasing the rate at which harmful substances carried by water penetrate into the coating. The core layer is copolymerized from butyl acrylate and cyclohexyl methacrylate, with a glass transition temperature controlled between -15 and 5°C, giving the coating good flexibility and elasticity, allowing it to adapt to thermal expansion and contraction deformation of outdoor substrates due to diurnal temperature variations. 4-Methacryloxy-2,2,6,6-Tetramethylpiperidine is also introduced into the core layer as a polymerizable hindered amine light stabilizer monomer to participate in copolymerization. The hindered amine groups are anchored to the polymer molecular chain through covalent bonds, which fundamentally avoids the migration and loss problems caused by the physical dispersion of traditional small molecule light stabilizers.

[0008] In this invention, the slow-release anti-aging microspheres use mesoporous silica loaded with composite antioxidants as the core and polycaprolactone as the coating shell. Mesoporous silica has a high specific surface area and ordered mesoporous channels, allowing for efficient loading of benzotriazole UV absorbers and hindered phenolic antioxidants into the pores through physical adsorption, achieving high-capacity storage and nanoscale dispersion of the antioxidants. The polycaprolactone coating shell can slowly hydrolyze and degrade in the slightly alkaline environment of the coating film. The ester bond breaking rate is basically synchronized with the aging process of the coating film, enabling long-term controlled slow release of the antioxidants. In the early stages of coating aging, the surface shell remains intact, and the antioxidants stored in the mesoporous channels are not washed away by rainwater. As the coating film is exposed outdoors for longer periods, the shell gradually hydrolyzes and thins, and the antioxidants stored in the channels are released in an orderly manner, continuously replenishing the antioxidants consumed on the coating surface and extending the effective protection period. Meanwhile, the mesoporous silica inorganic framework itself has excellent UV stability and chemical inertness, and will not undergo photochemical degradation or discoloration during long-term outdoor exposure.

[0009] In this invention, the ultraviolet shielding filler adopts a structure design of cerium dioxide coated with nano-zinc oxide. The nano-zinc oxide possesses wide bandgap semiconductor properties (bandgap of approximately 3.37 eV), exhibiting strong absorption capability for mid-wave and short-wave ultraviolet light with wavelengths below 370 nm. It converts ultraviolet light energy into harmlessly dissipated heat energy through electronic transitions. The cerium dioxide coating layer has multiple functions, including: cerium dioxide has a bandgap of approximately 3.1 eV, absorbing ultraviolet light with wavelengths below 400 nm, complementing the absorption range of zinc oxide and broadening the ultraviolet shielding band; cerium ions in cerium dioxide can... + and Ce 4+ It exhibits reversible transformation and unique redox cycle capability, which can catalyze the decomposition of peroxide free radicals generated on the coating surface, thus acting as an antioxidant. The cerium dioxide coating layer effectively isolates the direct contact between nano zinc oxide and the fluorocarbon core-shell emulsion, preventing the degradation of the organic components of the emulsion caused by the photocatalytic activity of zinc oxide.

[0010] In this invention, the film-forming aid is used to reduce the minimum film-forming temperature of the fluorocarbon core-shell emulsion shell layer, so that the polymer particles can fully deform and fuse to form a continuous film layer at the construction temperature, thereby avoiding coating cracking or powdering problems caused by poor film formation.

[0011] In this invention, the defoamer is used to eliminate air bubbles introduced during the coating production process, preventing air bubbles from forming pinholes or pore defects in the coating after construction, and ensuring the continuity and density of the coating structure and the reliability of its waterproof performance.

[0012] In this invention, the thixotropic lubricant is used to adjust the rheological properties of the coating, giving the coating good thixotropic properties, so that it maintains high viscosity in a static state, preventing the slow-release anti-aging microspheres and UV-shielding fillers from settling and stratifying during storage; the viscosity decreases under construction shear, making it easy to apply by scraping, rolling or spraying; the viscosity recovers quickly after construction, avoiding sagging during vertical construction.

[0013] Preferably, the film-forming aid is selected from one or both of dipropylene glycol butyl ether or decyl alcohol ester.

[0014] Preferably, the defoamer is selected from one or both of mineral oil defoamers and organosilicon defoamers.

[0015] Preferably, the thixotropic lubricant is selected from one or both of cellulose ethers or bentonite.

[0016] Preferably, the preparation method of the fluorocarbon core-shell emulsion includes the following steps: S1. Sodium dodecyl sulfate, alkylphenol polyoxyethylene ether, water, butyl acrylate and cyclohexyl methacrylate are mixed and sheared and emulsified at 25~35℃ to obtain a core layer pre-emulsion. S2. Heat the core layer pre-emulsion to 70~80℃, add ammonium persulfate aqueous solution, and keep the reaction at the temperature to obtain the core layer emulsion. S3. After mixing and dissolving trifluoroethyl methacrylate, methyl methacrylate and polymerizable hindered amine light stabilizer monomer, add them to the core layer emulsion, heat to 75~85℃, add ammonium persulfate aqueous solution, keep the reaction at the temperature, cool, and obtain fluorocarbon core-shell emulsion.

[0017] S1, by limiting the mass ratio of sodium dodecyl sulfate and alkylphenol polyoxyethylene ether, enables the anionic emulsifier to disperse monomer droplets through charge repulsion, while the nonionic emulsifier further encapsulates the particles through steric hindrance. The combination of the two improves the stability of the core layer pre-emulsion and avoids the pre-emulsion from separating or breaking.

[0018] By limiting the temperature of the heat preservation reaction, S2 can ensure that ammonium persulfate generates free radicals at a suitable decomposition rate at that temperature, which can smoothly initiate the polymerization reaction of butyl acrylate and cyclohexyl methacrylate, resulting in uniform particle size of the core polymer particles and controllable glass transition temperature.

[0019] By limiting the mass ratio of trifluoroethyl methacrylate to methyl methacrylate, S3 enables the shell to form a continuous and dense fluoropolymer network during film formation, balancing shell hardness and hydrophobic properties. 4-Methacryloxy-2,2,6,6-tetramethylpiperidine chemically anchors the hindered amine groups to the shell polymer molecular chain through a copolymerization reaction, preventing the migration and loss of traditional physically added light stabilizers to the surface during use.

[0020] Preferably, in S1, the mass ratio of sodium dodecyl sulfate, alkylphenol polyoxyethylene ether, water, butyl acrylate and cyclohexyl methacrylate is 0.3~0.8:0.2~0.5:15~25:5~10:2~5.

[0021] Furthermore, the mass ratio of butyl acrylate to cyclohexyl methacrylate is limited to 5~10:2~5, and the glass transition temperature of the core layer after copolymerization is controlled at -15~5℃. Within this temperature range, the coating film has good flexibility and elasticity, and can adapt to the thermal expansion and contraction deformation of outdoor substrates caused by the temperature difference between day and night.

[0022] Preferably, in S1, the rotation speed of the shear emulsification is 1200~1800 r / min, and the time is 15~30 min.

[0023] Preferably, in S2, the mass ratio of the core layer pre-emulsion to the ammonium persulfate aqueous solution is 1:0.01~0.03, and the mass concentration of the ammonium persulfate aqueous solution is 5%~10%.

[0024] Furthermore, the mass concentration of the ammonium persulfate aqueous solution is limited to 5% to 10%. Within this concentration range, it can ensure that the initiator is fully dissolved in water and decomposes at an appropriate rate to generate free radicals, thus maintaining the stable progress of the polymerization reaction, while avoiding excessively high concentrations that could lead to excessively fast reaction rates or localized burst polymerization.

[0025] Preferably, in S2, the heat preservation reaction time is 1~2 hours.

[0026] Preferably, in S3, the mass ratio of trifluoroethyl methacrylate, methyl methacrylate, polymerizable hindered amine light stabilizer monomer, core emulsion and ammonium persulfate aqueous solution is 1:0.4~0.8:0.05~0.15:3.5~13:0.01~0.3, and the mass concentration of the ammonium persulfate aqueous solution is 5%~10%.

[0027] Furthermore, the mass ratio of the total mass of the shell layer monomers to the mass of the core layer emulsion is limited to 0.15~0.4:1. Within this range, the shell layer can uniformly and completely coat the surface of the core layer particles, forming a clear core-shell structure. If the shell layer is too thin, the weather protection effect will be insufficient; if the shell layer is too thick, the coating hardness will be too high, resulting in a decrease in flexibility.

[0028] Preferably, in step S3, the heat preservation reaction time is 1.5 to 3 hours.

[0029] Preferably, the polymerizable hindered amine light stabilizer monomer is 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine.

[0030] Preferably, the preparation method of the sustained-release anti-aging microspheres includes the following steps: Step 1: Mix polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, hydrochloric acid aqueous solution, 1,3,5-trimethylbenzene and tetraethyl orthosilicate, and stir at 35~45℃. Then continue stirring to carry out the reaction. After centrifugation, washing, drying and calcination, mesoporous silica is obtained. Step 2: Mix benzotriazole UV absorber, hindered phenolic antioxidant, acetone and mesoporous silica, disperse evenly by ultrasonication, impregnate under vacuum conditions, remove and dry to obtain mesoporous silica loaded with composite antioxidant. Step 3: After mixing the mesoporous silica, dichloromethane and polycaprolactone loaded with the composite antioxidant, the mixture is ultrasonically dispersed and stirred to dissolve. Then, under stirring conditions, an aqueous solution of polyvinyl alcohol is added for emulsification. Water is then added and stirring is continued to evaporate and remove dichloromethane. After centrifugation, washing with water and drying, slow-release antioxidant microspheres are obtained.

[0031] In step one, the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer acts as a structure-directing agent, self-assembling with the tetraethyl orthosilicate hydrolysis product under acidic conditions through hydrogen bonding and electrostatic interactions to form an ordered mesoscopic structure. 1,3,5-trimethylbenzene acts as a pore-expanding agent, effectively increasing the mesopore size, making it suitable for loading benzotriazole UV absorbers and hindered phenolic antioxidants with larger molecular sizes. After calcination to remove the template agent, a mesoporous silica support with ordered mesoporous channels and a high specific surface area is obtained.

[0032] Step two, through vacuum impregnation, effectively removes air from the mesoporous silica channels, allowing the acetone antioxidant solution to penetrate deep into the channels under vacuum negative pressure, achieving efficient loading of the antioxidant. Acetone solvent has good volatility, is easily removed after drying, and does not remain in the channels.

[0033] In step three, polycaprolactone can slowly hydrolyze and degrade in the slightly alkaline environment of the coating film. The ester bond breaking rate is basically synchronized with the aging process of the coating film, achieving long-term controlled release of the antioxidant. Polyvinyl alcohol acts as an emulsifier and dispersant stabilizer, enabling polycaprolactone to spread evenly on the surface of mesoporous silica and form a complete coating shell.

[0034] Preferably, in step one, the mass ratio of the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, hydrochloric acid aqueous solution, 1,3,5-trimethylbenzene and tetraethyl orthosilicate is 1:80~120:2~4:3~6, and the concentration of the hydrochloric acid aqueous solution is 1~3 mol / L.

[0035] Furthermore, the concentration of the hydrochloric acid aqueous solution is limited to 1~3 mol / L. Within this concentration range, the pH value of the system can be maintained in the optimal acidic range for the hydrolysis and condensation of ethyl silicate, which is conducive to the formation of an ordered mesoscopic structure rather than amorphous silica.

[0036] Preferably, in step one, the stirring treatment at 35~45℃ takes 2~4 hours and the stirring speed is 400~800 r / min; the continued stirring takes 20~30 hours and the stirring speed is 400~800 r / min.

[0037] Preferably, in step one, the calcination temperature is 500~600℃ and the time is 4~8h.

[0038] Furthermore, the calcination temperature is limited to 500~600℃. Within this temperature range, the organic template agent can be fully oxidized, decomposed, and removed, while maintaining the integrity of the mesoporous framework structure and avoiding the collapse of mesoporous channels due to excessively high temperatures.

[0039] Preferably, in step two, the mass-to-volume ratio of the benzotriazole UV absorber, the hindered phenolic antioxidant, acetone, and mesoporous silica is (0.2~0.4) g : (0.15~0.35) g : (100~200) mL : 1 g, wherein the benzotriazole UV absorber is 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, and the hindered phenolic antioxidant is pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0040] Furthermore, the mass ratio of benzotriazole UV absorbers to hindered phenolic antioxidants is limited to 1:0.5~1.5. The two work synergistically: the UV absorbers absorb harmful UV light and convert it into heat energy, while the hindered phenolic antioxidants capture free radicals and block the oxidation chain reaction. This synergistic effect of UV shielding and free radical scavenging delays coating aging.

[0041] Preferably, in step two, the vacuum degree of the vacuum condition is -0.08 to -0.1 MPa, and the immersion time is 60 to 120 minutes.

[0042] Preferably, in step three, the mass-to-volume ratio of the mesoporous silica, dichloromethane, polycaprolactone, polyvinyl alcohol aqueous solution, and water loaded with the composite antioxidant is 1g:(20~40)mL:(0.5~1.5)g:(60~100)mL:(120~400)mL, and the mass concentration of the polyvinyl alcohol aqueous solution is 0.5%~2%.

[0043] Furthermore, the amount of polycaprolactone is limited to 0.5~1.5g per gram of mesoporous silica loaded with antioxidant. Within this range, a complete and uniform coating layer can be formed, while avoiding the antioxidant being released too slowly in the early stage due to an excessively thick coating layer or prematurely leaking due to an excessively thin coating layer.

[0044] Preferably, in step three, the stirring speed for emulsification is 600~1000 r / min, and the time is 10~30 min.

[0045] Preferably, the method for preparing the ultraviolet shielding filler includes the following steps: Step 1: Cerium acetate, anhydrous ethanol and nano zinc oxide are mixed and ultrasonically dispersed. Ammonia is added to adjust the pH to 9-11. Precipitation reaction is carried out at 50-70℃. Then water is added and stirring is continued to carry out hydrolysis. After centrifugation, washing and drying, precursor-coated zinc oxide powder is obtained. Step 2: The precursor-coated zinc oxide powder is calcined in air, cooled, and then ground to obtain cerium dioxide-coated zinc oxide powder.

[0046] Step one, by limiting the pH range adjusted with ammonia, provides an alkaline environment for the hydrolysis of cerium acetate, allowing the cerium hydroxide precursor to uniformly precipitate on the surface of the nano-zinc oxide particles, forming a coating layer. Adding water further promotes the complete hydrolysis of cerium acetate, resulting in a dense and uniform coating layer.

[0047] Step two, by limiting the temperature and atmosphere of the calcination treatment, can convert the cerium hydroxide precursor into the cerium dioxide crystalline phase. In an air atmosphere, cerium exists as Ce. 4+ The main component is cerium dioxide, which forms a cerium dioxide coating layer with ultraviolet absorption and redox activity.

[0048] Preferably, in step one, the average particle size of the nano-zinc oxide is 20~80nm.

[0049] Furthermore, the particle size of the nano zinc oxide is limited to 20~80nm. Within this particle size range, zinc oxide has a high specific surface area and UV absorption efficiency, which can effectively absorb UV light and also serve as a coating core to be uniformly dispersed in the reaction system.

[0050] Preferably, in step one, the mass-to-volume ratio of cerium acetate, anhydrous ethanol, nano zinc oxide, and water is (0.5~2.0) g : (200~400) mL : 10 g : (100~600) mL.

[0051] Furthermore, the amount of cerium acetate is limited to 0.5~2.0g per 10g of nano zinc oxide. Within this range, the thickness of the cerium dioxide coating layer is moderate, which can effectively isolate the photocatalytic active center of zinc oxide and form a complete ultraviolet shielding and antioxidant functional layer on the surface of zinc oxide.

[0052] Preferably, in step one, the stirring speed of the precipitation reaction is 600~1000 r / min, and the time is 2~4 h.

[0053] Preferably, in step one, the stirring speed for hydrolysis is 600~1000 r / min, and the time is 1~3 h.

[0054] Preferably, in step two, the calcination treatment is carried out at a temperature of 400~600℃ for 2~4 hours.

[0055] Furthermore, the calcination temperature is limited to 400~600℃. Within this temperature range, cerium hydroxide can be fully dehydrated and converted into cerium dioxide, while maintaining the particle size and morphology of the nanoparticles and avoiding excessive temperature from causing particle sintering and a decrease in specific surface area.

[0056] A second aspect of the present invention provides a method for preparing the aging-resistant and waterproof building coating described in the foregoing solution, comprising the following steps: Step 1: Mix water, film-forming aid and defoamer, then add fluorocarbon core-shell emulsion while stirring at 400~800 r / min, and continue stirring for 15~30 min to obtain liquid premix; Step 2: Under stirring conditions of 200~400r / min, add the slow-release anti-aging microspheres, UV shielding filler and thixotropic lubricant to the liquid premix in sequence, and stir for 10~20min to obtain the anti-aging waterproof building coating.

[0057] Step 1, by limiting the stirring speed and time, ensures that the film-forming aid is fully dissolved and evenly penetrates the surface of the fluorocarbon core-shell emulsion particles, promoting the fusion of the emulsion particles into a film after construction. At the same time, the defoamer is evenly dispersed to eliminate air bubbles that may be introduced during subsequent stirring.

[0058] Step 2, by limiting the stirring speed to a low range, avoids the shear force generated by high-speed stirring from damaging the polycaprolactone coating layer of the slow-release antioxidant microspheres, ensuring the integrity and sealing of the microspheres in the finished coating, and guaranteeing the reliability of the antioxidant's slow-release function. Simultaneously, the lower stirring speed allows the slow-release antioxidant microspheres, UV-shielding filler, and thixotropic lubricant to be uniformly dispersed in the liquid premix, preventing localized aggregation.

[0059] The third aspect of this invention provides the application of the aforementioned aging-resistant and waterproof building coating in the field of waterproofing.

[0060] When applying the aforementioned anti-aging and waterproof building coating to exposed roofs, exterior walls, bridges, balconies, and other substrates, it can be applied by scraping, rolling, or spraying. After application, the moisture and film-forming aids in the coating work together to promote the fusion of fluorocarbon core-shell emulsion particles, forming a continuous and dense coating film. The fluorinated segments of the shell layer accumulate on the coating surface, forming a low surface energy hydrophobic layer. During long-term outdoor exposure, the fluorocarbon shell layer on the coating surface resists UV degradation and rainwater erosion with the strong bond energy of the CF bonds and the low surface energy characteristics. The slow-release anti-aging microspheres inside the coating continuously release benzotriazole UV absorbers and hindered phenolic antioxidants through the slow hydrolysis of the polycaprolactone shell layer, replenishing the anti-aging agents consumed on the coating surface. The UV-shielding filler protects the coating film through the synergistic UV absorption and free radical decomposition effects of cerium dioxide and zinc oxide, providing both physical shielding and chemical removal. At room temperature, the surface drying time is 2 hours and the actual drying time is 8 hours. After 1000 hours of xenon lamp aging, the adhesion strength retention rate is 85%, and the coating surface shows no powdering or cracking.

[0061] In summary, the present invention provides an aging-resistant and waterproof building coating, which, by weight parts, comprises fluorocarbon core-shell emulsion, slow-release anti-aging microspheres, UV-shielding filler, film-forming aid, defoamer, thixotropic lubricant, and water. The aging-resistant waterproof building coating provided by this invention provides the polymer's aging resistance through the intrinsic UV resistance of the CF bonds in the fluorocarbon core-shell emulsion and the anchoring of polymerizable hindered amines. It achieves long-term sustained-release replenishment of antioxidants through the mesoporous loading of slow-release antioxidant microspheres and the controlled hydrolysis of polycaprolactone. Furthermore, it constructs an inorganic physicochemical dual-effect barrier through cerium dioxide-coated zinc oxide in the UV-shielding filler, synergistically supporting UV absorption and free radical decomposition. The synergistic effect of each component constructs a multi-level aging-resistant protection system from three dimensions: polymer weather resistance, long-term sustained release of antioxidants, and inorganic UV shielding. This solves the problems of easy migration and loss of small-molecule antioxidants and rapid degradation of the waterproof function of traditional exposed waterproof coatings. The coating exhibits excellent UV aging resistance and waterproof performance under long-term outdoor exposure conditions, meeting the comprehensive needs of outdoor waterproofing projects such as exposed roofs, exterior walls, bridges, and balconies for long-life protection and low maintenance costs.

[0062] Meanwhile, the present invention also provides a method for preparing an aging-resistant waterproof building coating. This preparation method can be completed by step mixing, without the need for special high-temperature or high-pressure equipment, is easy to operate, has good storage stability, and is suitable for large-scale production.

[0063] In addition, the present invention also provides an application method of aging-resistant waterproof building coating in the field of waterproofing. The coating can be applied to various outdoor building substrates through conventional scraping, rolling or spraying processes in the field. The resulting aging-resistant waterproof coating can be directly used for outdoor waterproofing projects such as exposed roofs, exterior walls, bridges and balconies, to achieve long-term protection of the building substrate and avoid structural damage caused by ultraviolet aging and water erosion. Detailed Implementation

[0064] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are merely one embodiment of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0065] The chemical reagents used in the embodiments and comparative examples of this invention are all commercially available products and have not undergone further purification or processing.

[0066] Example 1 This embodiment provides an aging-resistant and waterproof building coating and its preparation method, specifically including the following: The aging-resistant and waterproof building coating comprises the following components by weight: 40 parts of fluorocarbon core-shell emulsion, 15 parts of slow-release anti-aging microspheres, 5 parts of UV-shielding filler, 2 parts of film-forming aid, 0.1 parts of defoamer, 0.1 parts of thixotropic lubricant, and 5 parts of water; The film-forming aid is dipropylene glycol butyl ether; The defoamer is a mineral oil defoamer; The thixotropic lubricant is a cellulose ether.

[0067] The preparation method of the fluorocarbon core-shell emulsion includes the following steps: S1. Mix 0.3g sodium dodecyl sulfate, 0.2g alkylphenol polyoxyethylene ether, 15g water, 5g butyl acrylate and 2g cyclohexyl methacrylate, and shear emulsify at 25℃ and 1200r / min for 15min to obtain core layer pre-emulsion. S2. Heat 22.5g of the core layer pre-emulsion to 70°C, add 0.23g of 5% ammonium persulfate aqueous solution, and keep the reaction at this temperature for 1 hour to obtain the core layer emulsion. S3. Mix and dissolve 2.8g of trifluoroethyl methacrylate, 1.1g of methyl methacrylate and 0.14g of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, and add the mixture to the core emulsion. Heat the mixture to 75°C, add 0.02g of 5% ammonium persulfate aqueous solution, keep the mixture at this temperature for 1.5h, and then cool to obtain a fluorocarbon core-shell emulsion.

[0068] The preparation method of the sustained-release anti-aging microspheres includes the following steps: Step 1: Mix 1g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, 80mL of 1mol / L hydrochloric acid aqueous solution, 2g of 1,3,5-trimethylbenzene and 3g of tetraethyl orthosilicate, and stir at 35℃ and 400r / min for 2h. Then continue to react at 400r / min for 20h. After centrifugation, washing and drying, calcine at 500℃ for 4h to obtain mesoporous silica. Step 2: Mix and dissolve 0.2g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 0.15g of pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 100mL of acetone, add 1g of the mesoporous silica, ultrasonically disperse evenly, impregnate under a vacuum of -0.08MPa for 60min, remove and dry to obtain mesoporous silica loaded with composite antioxidant; Step 3: Mix 1g of the mesoporous silica loaded with the composite antioxidant and 20mL of dichloromethane, then ultrasonically disperse the mixture evenly. Add 0.5g of polycaprolactone, stir until dissolved, and then add 60mL of 0.5% polyvinyl alcohol aqueous solution under stirring at 600r / min for 10min to emulsify. Then add 120mL of water and continue stirring to evaporate and remove the dichloromethane. After centrifugation, washing with water, and drying, the slow-release antioxidant microspheres are obtained.

[0069] The preparation method of the ultraviolet shielding filler includes the following steps: Step 1: Dissolve 0.5g of cerium acetate in 200mL of anhydrous ethanol, add 10g of nano zinc oxide, and ultrasonically disperse until uniform. Adjust the pH to 9 with ammonia water, and carry out a precipitation reaction at 50℃ and 600r / min for 2h. Then add 100mL of water and continue hydrolysis at 600r / min for 1h. After centrifugation, washing, and drying, obtain precursor-coated zinc oxide powder; wherein the average particle size of the nano zinc oxide is 20nm. Step 2: The precursor-coated zinc oxide powder is calcined in air at 400°C for 2 hours, cooled, and then ground to obtain cerium dioxide-coated zinc oxide powder.

[0070] The preparation method of the aging-resistant and waterproof building coating includes the following steps: Step 1: Mix 5g water, 2g dipropylene glycol butyl ether and 0.1g mineral oil defoamer, then add 40g fluorocarbon core-shell emulsion while stirring at 400r / min, and continue stirring for 15min to obtain liquid premix. Step 2: Under stirring conditions of 200 r / min, 15 g of slow-release anti-aging microspheres, 5 g of UV-shielding filler and 0.1 g of cellulose ether are added to the liquid premix in sequence and stirred for 10 min to obtain an anti-aging waterproof building coating.

[0071] Example 2 This embodiment provides an aging-resistant and waterproof building coating and its preparation method, specifically including the following: The aging-resistant and waterproof building coating comprises the following components by weight: 55 parts of fluorocarbon core-shell emulsion, 30 parts of slow-release anti-aging microspheres, 10 parts of UV-shielding filler, 5 parts of film-forming aid, 0.5 parts of defoamer, 0.5 parts of thixotropic lubricant, and 15 parts of water; The film-forming aid is alcohol ester dodecyl; The defoamer is an organosilicone defoamer; The thixotropic lubricant is bentonite.

[0072] The preparation method of the fluorocarbon core-shell emulsion includes the following steps: S1. Mix 0.8g sodium dodecyl sulfate, 0.5g alkylphenol polyoxyethylene ether, 25g water, 10g butyl acrylate and 5g cyclohexyl methacrylate, and shear emulsify at 35℃ and 1800r / min for 30min to obtain core layer pre-emulsion. S2. Heat 41.3g of the core layer pre-emulsion to 80°C, add 1.23g of 10% ammonium persulfate aqueous solution, and keep the reaction at this temperature for 2 hours to obtain the core layer emulsion. S3. Mix and dissolve 5.6g of trifluoroethyl methacrylate, 4.5g of methyl methacrylate and 0.84g of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, and add the mixture to the core emulsion. Heat the mixture to 85°C, add 0.33g of 10% ammonium persulfate aqueous solution, keep the mixture at this temperature for 3 hours, and then cool it to obtain a fluorocarbon core-shell emulsion.

[0073] The preparation method of the sustained-release anti-aging microspheres includes the following steps: Step 1: Mix 1g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, 120mL of 3mol / L hydrochloric acid aqueous solution, 4g of 1,3,5-trimethylbenzene and 6g of tetraethyl orthosilicate, and stir at 45℃ and 800r / min for 4h. Then continue to react at 800r / min for 30h. After centrifugation, washing and drying, calcine at 600℃ for 8h to obtain mesoporous silica. Step 2: Mix and dissolve 0.4g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 0.35g of pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 200mL of acetone, add 1g of the mesoporous silica, ultrasonically disperse evenly, impregnate for 120min under a vacuum of -0.1MPa, remove and dry to obtain mesoporous silica loaded with composite antioxidant; Step 3: Mix 1g of the mesoporous silica loaded with the composite antioxidant and 40mL of dichloromethane, then ultrasonically disperse the mixture evenly. Add 1.5g of polycaprolactone, stir until dissolved, and then add 100mL of 2% polyvinyl alcohol aqueous solution under stirring at 1000r / min for emulsification for 30min. Then add 400mL of water and continue stirring to evaporate and remove the dichloromethane. After centrifugation, washing with water, and drying, obtain the slow-release antioxidant microspheres.

[0074] The preparation method of the ultraviolet shielding filler includes the following steps: Step 1: Dissolve 2.0g of cerium acetate in 400mL of anhydrous ethanol, add 10g of nano zinc oxide, and ultrasonically disperse until uniform. Adjust the pH to 11 with ammonia water, and carry out a precipitation reaction at 70℃ and 1000r / min for 4h. Then add 600mL of water and continue hydrolysis at 1000r / min for 3h. After centrifugation, washing, and drying, obtain precursor-coated zinc oxide powder; wherein the average particle size of the nano zinc oxide is 80nm. Step 2: The precursor-coated zinc oxide powder is calcined in air at 600°C for 4 hours, cooled, and then ground to obtain cerium dioxide-coated zinc oxide powder.

[0075] The preparation method of the aging-resistant and waterproof building coating includes the following steps: Step 1: Mix 15g water, 5g alcohol ester dodecyl and 0.5g silicone defoamer, then add 55g fluorocarbon core-shell emulsion while stirring at 800r / min, and continue stirring for 30min to obtain liquid premix; Step 2: Under stirring conditions of 400 r / min, add 30 g of slow-release anti-aging microspheres, 10 g of UV-shielding filler and 0.5 g of bentonite to the liquid premix in sequence, stir for 20 min, and obtain an anti-aging waterproof building coating.

[0076] Example 3 This embodiment provides an aging-resistant and waterproof building coating and its preparation method, specifically including the following: The aging-resistant and waterproof building coating comprises the following components by weight: 48 parts of fluorocarbon core-shell emulsion, 22 parts of slow-release anti-aging microspheres, 7 parts of UV-shielding filler, 3.5 parts of film-forming aid, 0.3 parts of defoamer, 0.3 parts of thixotropic lubricant, and 10 parts of water; The film-forming aid is alcohol ester dodecyl; The defoamer is a mineral oil defoamer; The thixotropic lubricant is a cellulose ether.

[0077] The preparation method of the fluorocarbon core-shell emulsion includes the following steps: S1. Mix 0.55g sodium dodecyl sulfate, 0.35g alkylphenol polyoxyethylene ether, 20g water, 7.5g butyl acrylate and 3.5g cyclohexyl methacrylate, and shear emulsify at 30℃ and 1500r / min for 20min to obtain core layer pre-emulsion. S2. Heat 31.9g of the core layer pre-emulsion to 75°C, add 0.6g of 7% ammonium persulfate aqueous solution, and keep the reaction at this temperature for 1.5h to obtain the core layer emulsion. S3. Mix and dissolve 4.2g of trifluoroethyl methacrylate, 2.5g of methyl methacrylate and 0.42g of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, and add the mixture to the core emulsion. Heat the mixture to 80°C, add 0.12g of 7% ammonium persulfate aqueous solution, keep the mixture at this temperature for 2 hours, and then cool it to obtain a fluorocarbon core-shell emulsion.

[0078] The preparation method of the sustained-release anti-aging microspheres includes the following steps: Step 1: Mix 1g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, 100mL of 2mol / L hydrochloric acid aqueous solution, 3g of 1,3,5-trimethylbenzene and 4.5g of tetraethyl orthosilicate, and stir at 40℃ and 600r / min for 3h. Then continue to react at 600r / min for 25h. After centrifugation, washing and drying, calcine at 550℃ for 6h to obtain mesoporous silica. Step 2: Mix and dissolve 0.3g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 0.25g of pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 150mL of acetone, add 1g of the mesoporous silica, ultrasonically disperse evenly, impregnate for 90min under a vacuum of -0.09MPa, remove and dry to obtain mesoporous silica loaded with composite antioxidant; Step 3: Mix 1g of the mesoporous silica loaded with the composite antioxidant and 30mL of dichloromethane, then ultrasonically disperse the mixture. Add 1.0g of polycaprolactone and stir until dissolved. Then, under stirring at 800r / min, add 80mL of a 1.2% polyvinyl alcohol aqueous solution for emulsification for 20min. Then, add 260mL of water and continue stirring to evaporate and remove the dichloromethane. After centrifugation, washing with water, and drying, obtain the slow-release antioxidant microspheres.

[0079] The preparation method of the ultraviolet shielding filler includes the following steps: Step 1: Dissolve 1.2g of cerium acetate in 300mL of anhydrous ethanol, add 10g of nano zinc oxide, and ultrasonically disperse until uniform. Adjust the pH to 10 with ammonia water, and carry out a precipitation reaction at 60℃ and 800r / min for 3h. Then add 350mL of water and continue hydrolysis at 800r / min for 2h. After centrifugation, washing, and drying, obtain precursor-coated zinc oxide powder; wherein the average particle size of the nano zinc oxide is 50nm. Step 2: The precursor-coated zinc oxide powder is calcined in air at 500°C for 3 hours, cooled, and then ground to obtain cerium dioxide-coated zinc oxide powder.

[0080] The preparation method of the aging-resistant and waterproof building coating includes the following steps: Step 1: Mix 10g water, 3.5g alcohol ester twelve and 0.3g mineral oil defoamer, then add 48g fluorocarbon core-shell emulsion while stirring at 600r / min, and continue stirring for 20min to obtain liquid premix; Step 2: Under stirring conditions of 300 r / min, 22 g of slow-release anti-aging microspheres, 7 g of UV-shielding filler and 0.3 g of cellulose ether are added to the liquid premix in sequence and stirred for 15 min to obtain an anti-aging waterproof building coating.

[0081] Comparative Example 1 This comparative example provides a waterproof building coating and its preparation method, specifically including the following: The waterproof building coating comprises the following components by weight: The mixture consists of 40 parts of ordinary acrylic emulsion, 20 parts of calcium carbonate filler, 2 parts of film-forming aid, 0.1 parts of defoamer, 0.1 parts of thixotropic lubricant, and 5 parts of water. The film-forming aid is dipropylene glycol butyl ether; The defoamer is a mineral oil defoamer; The thixotropic lubricant is a cellulose ether.

[0082] The ordinary acrylic emulsion is a commercially available pure acrylic emulsion with a solid content of 50% and a glass transition temperature of approximately -10°C.

[0083] The preparation method of the waterproof building coating includes the following steps: Step 1: Mix 5g water, 2g dipropylene glycol butyl ether and 0.1g mineral oil defoamer, then add 40g ordinary acrylic emulsion while stirring at 400r / min, and continue stirring for 15min to obtain liquid premix. Step 2: Under stirring conditions of 200 r / min, 20 g of calcium carbonate filler and 0.1 g of cellulose ether are added sequentially to the liquid premix and stirred for 10 min to obtain a waterproof building coating.

[0084] Comparative Example 2 This comparative example provides a waterproof building coating and its preparation method, specifically including the following: The waterproof building coating comprises the following components by weight: 48 parts of fluorocarbon core-shell emulsion, 22 parts of blank mesoporous silica, 7 parts of UV shielding filler, 3.5 parts of film-forming aid, 0.3 parts of defoamer, 0.3 parts of thixotropic lubricant, and 10 parts of water; The film-forming aid is alcohol ester dodecyl; The defoamer is a mineral oil defoamer; The thixotropic lubricant is a cellulose ether.

[0085] The preparation method of the fluorocarbon core-shell emulsion is the same as in Example 3.

[0086] The preparation method of the ultraviolet shielding filler is the same as in Example 3.

[0087] The method for preparing the blank mesoporous silica includes the following steps: 1g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, 100mL of 2mol / L hydrochloric acid aqueous solution, and 3g 1,3,5-trimethylbenzene and 4.5 g of tetraethyl orthosilicate were mixed and stirred at 40 °C and 600 r / min for 3 h. The mixture was then stirred at 600 r / min for 25 h. After centrifugation, washing, and drying, the mixture was calcined at 550 °C for 6 h to obtain blank mesoporous silica.

[0088] The preparation method of the waterproof building coating includes the following steps: Step 1: Mix 10g water, 3.5g alcohol ester twelve and 0.3g mineral oil defoamer, then add 48g fluorocarbon core-shell emulsion while stirring at 600r / min, and continue stirring for 20min to obtain liquid premix; Step 2: Under stirring conditions of 300 r / min, 22 g of blank mesoporous silica, 7 g of UV shielding filler and 0.3 g of cellulose ether are added sequentially to the liquid premix and stirred for 15 min to obtain a waterproof building coating.

[0089] Comparative Example 3 This comparative example provides a waterproof building coating and its preparation method, specifically including the following: The waterproof building coating comprises the following components by weight: The mixture contains 48 parts of fluorocarbon core-shell emulsion, 0.55 parts of an additive composite antioxidant mixture, 21.45 parts of filler, 7 parts of UV-shielding filler, 3.5 parts of film-forming aid, 0.3 parts of defoamer, 0.3 parts of thixotropic lubricant, and 10 parts of water. The film-forming aid is alcohol ester dodecyl; The defoamer is a mineral oil defoamer; The thixotropic lubricant is a cellulose ether.

[0090] The preparation method of the fluorocarbon core-shell emulsion is the same as in Example 3.

[0091] The preparation method of the ultraviolet shielding filler is the same as in Example 3.

[0092] The compound antioxidant mixture is composed of 0.3g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole and 0.25g of pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid].

[0093] The filler is commercially available precipitated silica.

[0094] The preparation method of the waterproof building coating includes the following steps: Step 1: Mix 10g water, 3.5g alcohol ester dodecyl, 0.3g mineral oil defoamer and 0.55g compound antioxidant mixture, then add 48g fluorocarbon core-shell emulsion while stirring at 600r / min and continue stirring for 20min to obtain liquid premix. Step 2: Under stirring conditions of 300 r / min, 21.45 g of filler, 7 g of UV shielding filler and 0.3 g of cellulose ether are added to the liquid premix in sequence and stirred for 15 min to obtain waterproof building coating.

[0095] Comparative Example 4 This comparative example provides a waterproof building coating and its preparation method, specifically including the following: The waterproof building coating comprises the following components by weight: 48 parts of fluorocarbon core-shell emulsion, 22 parts of uncoated loaded anti-aging mesoporous silica, 7 parts of UV shielding filler, 3.5 parts of film-forming aid, 0.3 parts of defoamer, 0.3 parts of thixotropic lubricant, and 10 parts of water; The film-forming aid is alcohol ester dodecyl; The defoamer is a mineral oil defoamer; The thixotropic lubricant is a cellulose ether.

[0096] The preparation method of the fluorocarbon core-shell emulsion is the same as in Example 3.

[0097] The preparation method of the ultraviolet shielding filler is the same as in Example 3.

[0098] The preparation method of the uncoated loaded anti-aging mesoporous silica includes the following steps: Step 1: Mix 1g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, 100mL of 2mol / L hydrochloric acid aqueous solution, 3g of 1,3,5-trimethylbenzene and 4.5g of tetraethyl orthosilicate, and stir at 40℃ and 600r / min for 3h. Then continue to react at 600r / min for 25h. After centrifugation, washing and drying, calcine at 550℃ for 6h to obtain mesoporous silica. Step 2: Mix and dissolve 0.3g of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 0.25g of pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 150mL of acetone, add 1g of the mesoporous silica, and ultrasonically disperse until uniform. Impregnate for 90min under a vacuum of -0.09MPa, remove and dry to obtain uncoated loaded anti-aging mesoporous silica.

[0099] The preparation method of the waterproof building coating includes the following steps: Step 1: Mix 10g water, 3.5g alcohol ester twelve and 0.3g mineral oil defoamer, then add 48g fluorocarbon core-shell emulsion while stirring at 600r / min, and continue stirring for 20min to obtain liquid premix; Step 2: Under stirring conditions of 300 r / min, 22 g of uncoated loaded anti-aging mesoporous silica, 7 g of UV shielding filler and 0.3 g of cellulose ether are added sequentially to the liquid premix and stirred for 15 min to obtain a waterproof building coating.

[0100] Performance testing The aging resistance, waterproof performance, and storage stability of the coatings formed by curing the aging-resistant waterproof building coatings in Examples 1-3 and the waterproof building coatings in Comparative Examples 1-4 were tested. The test results are shown in Table 1.

[0101] The coating preparation process in Examples 1-3 and Comparative Examples 1-4 specifically includes the following steps: the coating samples are applied to standard concrete slabs and aluminum slabs by scraping, the wet film thickness of the coating is controlled at 1.5 mm, and multiple parallel samples are prepared for each group.

[0102] The test of the bond strength retention rate after xenon lamp aging in the aging resistance test specifically includes the following steps: The dried concrete slab coating sample was placed in a xenon lamp aging test chamber, with the xenon lamp irradiance set to 60 W / m². 2(Wavelength range 300~400nm), blackboard temperature 65℃3℃, relative humidity inside the chamber 50%5%, continuous light irradiation and no spraying operation mode, after continuous aging for 1000h, the sample is taken out and the coating surface is observed for cracking, blistering, powdering or peeling, and the bonding strength after aging is measured. The bonding strength retention rate after 1000h aging is calculated according to the bonding strength retention rate (%) = (bonding strength after aging / initial bonding strength)100%.

[0103] The detection of water absorption rate change after accelerated UV aging in the aging resistance test specifically includes the following steps: Take a fully dried coating sample, peel the coating completely off the concrete slab, cut a 50mm x 50mm coating sheet, and place it in a UV accelerated aging test chamber. Set the UV lamp power to 40W, the vertical distance between the lamp and the sample surface to 15cm, and the chamber temperature to 60℃-2℃. After continuous irradiation for 500h, take it out and immerse it in 25℃ deionized water for 24h. After taking it out, quickly absorb the surface moisture with filter paper and weigh the mass after immersion. At the same time, take the coating sheet from the same batch that has not been UV aged and determine the initial water absorption rate. Calculate the water absorption rate change rate after UV aging according to the formula: water absorption rate change rate (%) = (water absorption rate after aging - initial water absorption rate) / initial water absorption rate × 100%.

[0104] The bonding strength test in the waterproof performance test specifically includes the following steps: After the concrete slab coating sample has dried, a 40mm diameter steel pull-out head is vertically attached to the coating surface using epoxy resin adhesive. Once the adhesive has fully cured, the coating is cut along the circumference of the pull-out head down to the substrate. A pull-out tester is used to apply a vertical tensile force at a pulling rate of 5mm / min. The maximum tensile force at which the coating fails to peel off from the substrate is recorded. The bond strength (MPa) is calculated as: Maximum tensile force (N) / Pull-out area (mm²). 2 Calculate the bond strength.

[0105] The waterproof performance test, specifically the seepage resistance pressure test, includes the following steps: Take a sample of the concrete slab coating after it has dried, install it on the mortar permeability tester, seal and fix it, set the initial water pressure to 0.1 MPa and keep it constant for 1 hour, then increase the water pressure by 0.1 MPa every hour, and gradually increase the pressure. When the first water seepage point appears on the coating surface, record the previous water pressure value as the permeability pressure of the sample.

[0106] The water absorption rate test in the waterproof performance test specifically includes the following steps: Take a fully dried coating sample, peel the coating completely off the concrete slab, cut a 50mm x 50mm coating test piece, dry it in a 50℃ oven until constant weight, weigh the initial mass, then immerse it in 25℃ deionized water for 24 hours, take it out, quickly absorb the surface moisture with filter paper, weigh the mass after immersion, and calculate the water absorption rate of the coating according to the formula: water absorption rate (%) = (mass after immersion - initial mass) / initial mass × 100%.

[0107] The storage stability test specifically includes the following steps: Take a sealed paint sample and place it in an oven at 50℃-2℃ for 7 days. After removing it and cooling it to room temperature, open the can and observe whether the paint has clumping, layering, or gelling. Stir it with a glass rod to determine its workability. If there are no abnormalities and it can be stirred and applied normally, the storage stability is deemed to be qualified.

[0108] Table 1 Performance Test Results project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Bond strength retention rate after 1000h aging (%) 85 91 88 42 78 72 86 Change in water absorption rate after UV aging (%) 15 8 10 65 22 45 12 Initial bond strength (MPa) 1.3 1.6 1.5 0.4 1.4 1.4 1.5 Impermeability pressure (MPa) 0.7 0.9 0.8 0.2 0.8 0.7 0.8 Water absorption rate (%) 2.6 1.9 2.2 7.5 2.4 3.1 2.3 Storage stability qualified qualified qualified qualified qualified qualified Layered caking The above are all preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. An aging-resistant and waterproof building coating, characterized in that, By mass parts, it includes the following components: The mixture consists of 40-55 parts of fluorocarbon core-shell emulsion, 15-30 parts of slow-release anti-aging microspheres, 5-10 parts of UV-shielding filler, 2-5 parts of film-forming aid, 0.1-0.5 parts of defoamer, 0.1-0.5 parts of thixotropic lubricant, and 5-15 parts of water.

2. The aging-resistant and waterproof building coating according to claim 1, characterized in that, The preparation method of the fluorocarbon core-shell emulsion includes the following steps: S1. Sodium dodecyl sulfate, alkylphenol polyoxyethylene ether, water, butyl acrylate and cyclohexyl methacrylate are mixed and sheared and emulsified at 25~35℃ to obtain a core layer pre-emulsion. S2. Heat the core layer pre-emulsion to 70~80℃, add ammonium persulfate aqueous solution, and keep the reaction at the temperature to obtain the core layer emulsion. S3. After mixing and dissolving trifluoroethyl methacrylate, methyl methacrylate and polymerizable hindered amine light stabilizer monomer, add them to the core layer emulsion, heat to 75~85℃, add ammonium persulfate aqueous solution, keep the reaction at the temperature, cool, and obtain fluorocarbon core-shell emulsion.

3. The aging-resistant and waterproof building coating according to claim 2, characterized in that, In S1, the mass ratio of sodium dodecyl sulfate, alkylphenol polyoxyethylene ether, water, butyl acrylate, and cyclohexyl methacrylate is 0.3~0.8:0.2~0.5:15~25:5~10:2~5; and / or In S1, the rotation speed of the shear emulsification is 1200~1800 r / min, and the time is 15~30 min; and / or In S2, the mass ratio of the core layer pre-emulsion to the ammonium persulfate aqueous solution is 1:0.01~0.03, and the mass concentration of the ammonium persulfate aqueous solution is 5%~10%; and / or In S2, the heat preservation reaction time is 1-2 hours; and / or In S3, the mass ratio of trifluoroethyl methacrylate, methyl methacrylate, polymerizable hindered amine light stabilizer monomer, core emulsion, and ammonium persulfate aqueous solution is 1:0.4~0.8:0.05~0.15:3.5~13:0.01~0.3, and the mass concentration of the ammonium persulfate aqueous solution is 5%~10%; and / or In S3, the heat preservation reaction time is 1.5~3h; and / or The polymerizable hindered amine light stabilizer monomer is 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine.

4. The aging-resistant and waterproof building coating according to claim 1, characterized in that, The preparation method of the sustained-release anti-aging microspheres includes the following steps: Step 1: Mix polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, hydrochloric acid aqueous solution, 1,3,5-trimethylbenzene and tetraethyl orthosilicate, and stir at 35~45℃. Then continue stirring to carry out the reaction. After centrifugation, washing, drying and calcination, mesoporous silica is obtained. Step 2: Mix benzotriazole UV absorber, hindered phenolic antioxidant, acetone and mesoporous silica, disperse evenly by ultrasonication, impregnate under vacuum conditions, remove and dry to obtain mesoporous silica loaded with composite antioxidant. Step 3: After mixing the mesoporous silica, dichloromethane and polycaprolactone loaded with the composite antioxidant, the mixture is ultrasonically dispersed and stirred to dissolve. Then, under stirring conditions, an aqueous solution of polyvinyl alcohol is added for emulsification. Water is then added and stirring is continued to evaporate and remove dichloromethane. After centrifugation, washing with water and drying, slow-release antioxidant microspheres are obtained.

5. The aging-resistant and waterproof building coating according to claim 4, characterized in that, In step one, the mass ratio of the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, hydrochloric acid aqueous solution, 1,3,5-trimethylbenzene, and tetraethyl orthosilicate is 1:80~120:2~4:3~6, and the concentration of the hydrochloric acid aqueous solution is 1~3 mol / L; and / or In step one, the stirring treatment at 35~45℃ lasts for 2~4 hours at a speed of 400~800 r / min; the continued stirring lasts for 20~30 hours at a speed of 400~800 r / min; and / or In step one, the calcination temperature is 500~600℃, and the time is 4~8h; and / or In step two, the mass-to-volume ratio of the benzotriazole UV absorber, the hindered phenolic antioxidant, acetone, and mesoporous silica is 0.2~0.4g:0.15~0.35g:100~200mL:1g. The benzotriazole UV absorber is 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, and the hindered phenolic antioxidant is pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; and / or In step two, the vacuum level is -0.08 to -0.1 MPa, and the impregnation time is 60 to 120 minutes; and / or In step three, the mass-to-volume ratio of the mesoporous silica, dichloromethane, polycaprolactone, polyvinyl alcohol aqueous solution, and water loaded with the composite antioxidant is 1 g : (20~40) mL : (0.5~1.5) g : (60~100) mL : (120~400) mL, and the mass concentration of the polyvinyl alcohol aqueous solution is 0.5%~2%; and / or In step three, the stirring speed for emulsification is 600~1000 r / min, and the time is 10~30 min.

6. The aging-resistant and waterproof building coating according to claim 1, characterized in that, The preparation method of the ultraviolet shielding filler includes the following steps: Step 1: Cerium acetate, anhydrous ethanol and nano zinc oxide are mixed and ultrasonically dispersed. Ammonia is added to adjust the pH to 9-11. Precipitation reaction is carried out at 50-70℃. Then water is added and stirring is continued to carry out hydrolysis. After centrifugation, washing and drying, precursor-coated zinc oxide powder is obtained. Step 2: The precursor-coated zinc oxide powder is calcined in air, cooled, and then ground to obtain cerium dioxide-coated zinc oxide powder.

7. The aging-resistant and waterproof building coating according to claim 6, characterized in that, In step one, the average particle size of the nano-zinc oxide is 20~80 nm; and / or In step one, the mass-to-volume ratio of cerium acetate, anhydrous ethanol, nano zinc oxide, and water is (0.5~2.0) g : (200~400) mL : 10 g : (100~600) mL; and / or In step one, the stirring speed of the precipitation reaction is 600~1000 r / min, and the time is 2~4 h; and / or In step one, the stirring speed for hydrolysis is 600~1000 r / min, and the time is 1~3 h; and / or In step two, the calcination treatment is carried out at a temperature of 400~600℃ for 2~4 hours.

8. The aging-resistant and waterproof building coating according to claim 1, characterized in that, The film-forming aid is selected from one or two of dipropylene glycol butyl ether or dodecyl alcohol ester; and / or The defoamer is selected from one or both of mineral oil defoamers and silicone defoamers; and / or The thixotropic lubricant is selected from one or both of cellulose ethers or bentonite.

9. The method for preparing the aging-resistant and waterproof building coating according to any one of claims 1 to 8, characterized in that, Includes the following steps: Step 1: Mix water, film-forming aid and defoamer, then add fluorocarbon core-shell emulsion while stirring at 400~800 r / min, and continue stirring for 15~30 min to obtain liquid premix; Step 2: Under stirring conditions of 200~400r / min, add the slow-release anti-aging microspheres, UV shielding filler and thixotropic lubricant to the liquid premix in sequence, and stir for 10~20min to obtain an anti-aging waterproof building coating.

10. The application of the aging-resistant waterproof building coating according to any one of claims 1 to 8 in the field of waterproofing.