Highly water-resistant wall coating and method for preparing the same

Abstract

The application discloses a kind of high water-resistant wall coating and preparation method thereof, belong to wall coating technical field, with single-component modified polysilicon epoxy resin, polysiloxane, silane coupling agent KH550, water-based resin, cerium oxide powder, nano titanium dioxide powder, composite mildew inhibitor powder, dispersing agent, film-forming aid, defoaming agent, leveling agent and water are stirred and mixed, obtain high water-resistant wall coating;The high water-resistant wall coating of the application has good adhesion and water resistance, cold and hot cycle resistance after building exterior wall coating film, and the added composite mildew inhibitor powder has good migration resistance;Vacuum extraction is used to make the mildew inhibitor IPBC enter the hollow structure of sulfonated modified silicon dioxide powder, so as to coat the mildew inhibitor IPBC, slow-release effect is achieved, a layer of zinc nano metal organic framework is generated on the surface, which can further control the release rate of the mildew inhibitor IPBC.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of wall coating, and particularly relates to a high water-resistant wall coating and a preparation method thereof. BACKGROUND

[0002] In building engineering, wall waterproofing is a very important work, and the external wall waterproof coating can effectively prevent rainwater from penetrating into the house, thereby prolonging the service life.

[0003] Inorganic coating is a kind of coating, the main film-forming material of which is inorganic material, and the constituent parts usually cover inorganic polymers, specially treated metals and metal oxide nanomaterials, and rare earth ultrafine powders, which can form an inorganic polymer anticorrosive coating with physical and chemical protection functions on the surface of the building external wall after use, the anticorrosive coating is closely connected with the matrix by chemical bonds, which ensures long service life and reduces the occurrence of wall peeling and cracking, and the pollution to the environment during production and application is relatively small, which is safe and environmentally friendly.

[0004] However, the building external wall is affected by natural factors such as wind and rain, sunlight, etc., the mildew inhibitor will migrate and fail, and a large number of mold spots will still appear on the external wall after a long time of use, which is difficult to clean and causes trouble for subsequent maintenance. SUMMARY

[0005] The purpose of the application is to provide a high water-resistant wall coating and a preparation method thereof, which reduces the water resistance and migration resistance of the mildew inhibitor by adding a composite mildew inhibitor powder, thereby increasing the mildew resistance of the building external wall.

[0006] The purpose of the application can be achieved by the following technical solutions:

[0007] A preparation method of a high water-resistant wall coating, comprising the following steps:

[0008] The single-component modified polysilicon epoxy resin, the polysiloxane, the silane coupling agent KH550, the water-based resin, the cerium oxide powder, the nano titanium dioxide powder, the composite mildew inhibitor powder, the dispersing agent, the film-forming aid, the defoaming agent, the leveling agent and the water are stirred and mixed to obtain the high water-resistant wall coating.

[0009] Further, the mass ratio of the single-component modified polysilicon epoxy resin, the polysiloxane, the silane coupling agent KH550, the water-based resin, the cerium oxide powder, the nano titanium dioxide powder, the composite mildew inhibitor powder, the dispersing agent, the film-forming aid, the defoaming agent, the leveling agent and the water is 30-35:20-25:0.2-0.8:5-8:5-8:20-30:0.5-1.5:0.5-1:0.5-1:0.5-1:0.5-1:5-10.

[0010] Further, the composite mildew-proof agent powder is prepared by the following steps:

[0011] Step 1: monodisperse hollow nanosilica, (3-epoxypropoxy) propyl trimethoxysilane and anhydrous methanol are added into a reaction kettle and stirred and mixed, then polyethyleneimine powder is added into the reaction kettle, ultrasonic dispersion is performed for 30-40 min, then stirring is performed at 65-70°C for 5-6 h, centrifugal filtration is performed, the filter cake is washed with anhydrous methanol for 3-5 times, and vacuum drying is performed to obtain functionalized silica powder.

[0012] The polyethyleneimine is modified on the surface of the monodisperse hollow nanosilica to provide abundant amino groups for the functionalized silica powder.

[0013] Step 2: sodium m-carboxybenzenesulfonate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and MES buffer solution with a concentration of 50 mmol / L are added into a reaction kettle and stirred and mixed, then the pH value is adjusted to 5-6 by using hydrochloric acid with a concentration of 4 mol / L, stirring is performed at 20-25°C for 20-30 min, then the functionalized silica powder is added into the reaction kettle, the pH value is adjusted to 7.5 by using sodium hydroxide solution with a concentration of 0.1 mol / L, and stirring is continuously performed for 10-12 h, centrifugal filtration is performed, the filter cake is dispersed in 30-50 times mass of hydrochloric acid with a molar concentration of 0.1 mol / L, stirring is performed at 25-30°C for 8-10 h, centrifugal washing is performed for 3-5 times, the filter cake is vacuum dried to obtain sulfonated modified silica powder.

[0014] The carboxyl in the sodium m-carboxybenzenesulfonate reacts with the amino on the surface of the functionalized silica powder to form an amide, and then the sodium sulfonate is converted into a sulfonic acid group by using hydrochloric acid.

[0015] Step 3: the sulfonated modified silica powder, the mildew-proof agent IPBC, deionized water and anhydrous ethanol are added into a reaction kettle, stirring is performed at 800-1000 r / min for 10-15 min, ultrasonic dispersion is performed for 20-30 min, vacuum is extracted to-0.09 MPa, stirring is continuously performed for 1-1.5 h, centrifugal filtration is performed, the filter cake is washed with anhydrous ethanol for 2-3 times, and vacuum drying is performed to obtain the mildew-proof agent / nanosilica composite powder.

[0016] The modified sulfonated modified silica powder has good adsorption, which is helpful to combine the mildew-proof agent IPBC, then the vacuum extraction is used to make the mildew-proof agent IPBC enter the hollow structure of the sulfonated modified silica powder, so that the mildew-proof agent IPBC is coated to have a slow-release effect.

[0017] Step 4: The antifungal agent / nano-silicon dioxide composite powder, zinc nitrate hexahydrate and 80% mass dispersion methanol aqueous solution are added into a reaction kettle, stirred at 300-500 r / min for 20-30 min, then isophthalic acid, 3-amino-1,2,4-triazole and N,N-dimethylformamide are added, continue to stir for 5-10 min, and then stir and react at 105-115 DEG C for 70-75 h, centrifugal filtration, the filter cake is washed with anhydrous methanol for 2-3 times, and vacuum drying to obtain the composite antifungal agent powder.

[0018] The sulfonic acid group on the surface of the antifungal agent / nano-silicon dioxide composite powder can chelate zinc ions, and the carboxyl in isophthalic acid can coordinate with zinc ions, so that a layer of zinc nano-metal organic framework is generated on the surface of the antifungal agent / nano-silicon dioxide composite powder particles, the antifungal effect is improved, and the release rate of the antifungal agent IPBC is further controlled, the migration rate of the antifungal agent IPBC is reduced, and the antifungal effect of the composite antifungal agent powder is improved.

[0019] Further, the amount ratio of monodisperse hollow nano-silicon dioxide, (3-epoxypropoxy) propyl trimethoxysilane, anhydrous methanol and polyethyleneimine powder in step 1 is 1g:1.1-1.2g:12-15mL:1g.

[0020] Further, the amount ratio of sodium 5-carboxybenzenesulfonate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, MES buffer and functionalized silicon dioxide powder in step 2 is 0.3-0.5g:0.2-0.3g:0.2-0.3g:10-15mL:0.15-0.25g.

[0021] Further, the amount ratio of sulfonated modified silicon dioxide powder, antifungal agent IPBC, deionized water and anhydrous ethanol in step 3 is 1g:0.8-1g:40mL:10mL.

[0022] Further, the amount ratio of antifungal agent / nano-silicon dioxide composite powder, zinc nitrate hexahydrate, isophthalic acid, 3-amino-1,2,4-triazole, methanol aqueous solution and N,N-dimethylformamide in step 4 is 1g:5-6g:1.4-1.6g:3-3.3g:10mL:8-10mL.

[0023] The beneficial effects of the present application are:

[0024] The high water-resistant wall coating of the present application has good adhesion and water resistance, cold and hot cycle resistance after coating on the building outer wall, and the added composite antifungal agent powder has good migration resistance, which helps to increase the antifungal performance of the building outer wall.

[0025] The composite mildew-proof agent powder provided by the application takes monodisperse hollow nanosilica as a matrix, polyethylene imine is modified on the surface of the monodisperse hollow nanosilica, and the functionalized nanosilica powder is provided with abundant amino groups, the carboxyl groups in sodium 5-sulfosalicylate are used to react with the amino groups on the surface of the functionalized nanosilica powder to generate an amide, then the sodium sulfonate is converted into a sulfonic acid group by using hydrochloric acid, the modified sulfonated nanosilica powder has good adsorption, which is helpful to the combination of the mildew-proof agent IPBC, the vacuumizing mode is used to make the mildew-proof agent IPBC enter the hollow structure of the sulfonated nanosilica powder, so as to coat the mildew-proof agent IPBC and achieve the slow-release effect; the sulfonic acid groups on the surface of the mildew-proof agent / nanosilica composite powder can chelate zinc ions, the carboxyl groups in isophthalic acid are used to coordinate with the zinc ions, so as to generate a layer of zinc nano metal organic framework on the surface of the mildew-proof agent / nanosilica composite powder, improve the mildew-proof effect, further regulate the release rate of the mildew-proof agent IPBC, reduce the migration rate of the mildew-proof agent IPBC, and thus improve the mildew-proof effect of the composite mildew-proof agent powder. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, but not all the embodiments of the application. Based on the embodiments in the application, all the other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the application.

[0027] Embodiment 1: The embodiment provides a high water-resistant wall coating, which is prepared by the following steps:

[0028] S1: 10 kg of monodisperse hollow nanosilica, 11 kg of (3-epoxypropoxy) propyl trimethoxysilane and 120 L of anhydrous methanol are added into a reaction kettle and stirred and mixed, 10 kg of polyethylene imine powder is added into the reaction kettle, ultrasonic dispersion is performed for 30 min, then stirring is performed at 65 DEG C for 5 h, centrifugal filtration is performed, the filter cake is washed with anhydrous methanol for 3 times, and vacuum drying is performed, to obtain functionalized nanosilica powder.

[0029] S2: 900 g of sodium m-carboxybenzenesulfonate, 600 g of 1-ethyl-3-(3- dimethylaminopropyl) carbodiimide hydrochloride, 600 g of N-hydroxysuccinimide and 30 L of MES buffer solution with a concentration of 50 mmol / L were added into a reaction kettle and stirred and mixed, then the pH value was adjusted to 5 with hydrochloric acid with a concentration of 4 mol / L, and stirring was continued at 20 DEG C for 20 min, then 450 g of functionalized silicon dioxide powder was added into the reaction kettle, the pH value was adjusted to 7.5 with sodium hydroxide solution with a concentration of 0.1 mol / L, and stirring was continued for 10 h, then centrifugal filtration was performed, the filter cake was dispersed in 30 times the mass of hydrochloric acid with a molar concentration of 0.1 mol / L, stirring was continued at 25 DEG C for 8 h, and the filter cake was washed by centrifugation for 3 times, and the filter cake was vacuum dried to obtain sulfonated modified silicon dioxide powder.

[0030] S3: 400 g of sulfonated modified silicon dioxide powder, 320 g of antifungal agent IPBC, 16 L of deionized water and 4 L of anhydrous ethanol were added into a reaction kettle, stirring was performed at 800 r / min for 10 min, ultrasonic dispersion was performed for 20 min, vacuum was drawn to -0.09 MPa, stirring was continued for 1 h, centrifugal filtration was performed, the filter cake was washed with anhydrous ethanol for 2 times, and vacuum drying was performed to obtain antifungal agent / nano-silicon dioxide composite powder.

[0031] S4: 400 g of antifungal agent / nano-silicon dioxide composite powder, 2 kg of zinc nitrate hexahydrate and 4 L of methanol aqueous solution with a mass fraction of 80% were added into a reaction kettle, stirring was performed at 300 r / min for 20 min, then 560 g of isophthalic acid, 1.2 kg of 3-amino-1, 2, 4-triazole and 3.2 L of N, N-dimethylformamide were added, stirring was continued for 5 min, and stirring reaction was performed at 105 DEG C for 70 h, then centrifugal filtration was performed, the filter cake was washed with anhydrous methanol for 2 times, and vacuum drying was performed to obtain composite antifungal agent powder.

[0032] S5: 12 kg of one-component modified polysilicone epoxy resin, 8 kg of polysiloxane, 80 g of silane coupling agent KH550, 2 kg of water-based resin, 2 kg of cerium oxide powder, 8 kg of nano-titanium dioxide powder, 200 g of composite antifungal agent powder, 200 g of dispersing agent, 200 g of film-forming aid, 200 g of defoaming agent, 200 g of leveling agent and 2 kg of water were stirred and mixed to obtain high water-resistant wall coating.

[0033] Example 2: The present example provides a kind of high water-resistant wall coating, which is prepared by the following steps:

[0034] S1: 10 kg of monodisperse hollow nanosilica, 11.5 kg (3- glycidoxypropyl) trimethoxysilane and 135 L of anhydrous methanol were added to a reaction kettle and stirred and mixed, then 10 kg of polyethyleneimine powder was added to the reaction kettle and ultrasonic dispersed for 35 min, then stirred at 68°C for 5.5 h, centrifugal filtration, the filter cake was washed with anhydrous methanol for 4 times, vacuum dried to obtain functionalized silica powder.

[0035] S2: 1300 g of sodium m-carboxybenzenesulfonate, 750 g of 1-ethyl-3-(3- dimethylaminopropyl) carbodiimide hydrochloride, 750 g of N-hydroxysuccinimide and 40 L of MES buffer solution with a concentration of 50 mmol / L were added to a reaction kettle and stirred and mixed, then the pH value was adjusted to 5.5 with hydrochloric acid with a concentration of 4 mol / L, stirred at 22°C for 25 min, then 600 g of functionalized silica powder was added to the reaction kettle, the pH value was adjusted to 7.5 with sodium hydroxide solution with a concentration of 0.1 mol / L, continued to stir for 11 h, centrifugal filtration, the filter cake was dispersed in 40 times mass of hydrochloric acid with a molar concentration of 0.1 mol / L, stirred at 28°C for 9 h, centrifugal washed for 4 times, the filter cake was vacuum dried to obtain sulfonated modified silica powder.

[0036] S3: 400 g of sulfonated modified silica powder, 360 g of antifungal agent IPBC, 16 L of deionized water and 4 L of anhydrous ethanol were added to a reaction kettle, stirred at 900 r / min for 12 min, ultrasonic dispersed for 25 min, vacuumed to-0.09 MPa, continued to stir for 1.2 h, centrifugal filtration, the filter cake was washed with anhydrous ethanol for 2 times, vacuum dried to obtain antifungal agent / nanosilica composite powder.

[0037] S4: 400 g of antifungal agent / nanosilica composite powder, 2.2 kg of zinc nitrate hexahydrate and 4 L of methanol aqueous solution with a mass fraction of 80% were added to a reaction kettle, stirred at 400 r / min for 25 min, then 600 g of isophthalic acid, 1.25 kg of 3-amino-1,2,4-triazole and 3.6 L of N,N-dimethylformamide were added, continued to stir for 8 min, stirred at 110°C for 72 h, centrifugal filtration, the filter cake was washed with anhydrous methanol for 2 times, vacuum dried to obtain composite antifungal agent powder.

[0038] S5: 13 kg of one-component modified polysilicone epoxy resin, 9 kg of polysiloxane, 150 g of silane coupling agent KH550, 3 kg of water-based resin, 2.5 kg of cerium oxide powder, 10 kg of nanometer titanium dioxide powder, 400 g of composite antifungal agent powder, 300 g of dispersing agent, 300 g of film-forming aid, 300 g of defoaming agent, 300 g of leveling agent and 3 kg of water were stirred and mixed to obtain high water-resistant wall coating.

[0039] Example 3: The present embodiment provides a high water-resistant wall coating, which is prepared by the following steps:

[0040] S1: 10 kg of monodisperse hollow nanosilica, 12 kg of (3- glycidoxypropyl)trimethoxysilane and 150 L of anhydrous methanol were added to a reaction kettle and stirred and mixed, then 10 kg of polyethyleneimine powder was added to the reaction kettle, ultrasonic dispersion was performed for 40 min, then stirring was performed at 70 °C for 5-6 h, centrifugal filtration was performed, the filter cake was washed with anhydrous methanol for 5 times, and vacuum drying was performed to obtain functionalized silica powder.

[0041] S2: 1500 g of sodium m-carboxybenzenesulfonate, 900 g of 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide hydrochloride, 900 g of N-hydroxysuccinimide and 45 L of MES buffer solution with a concentration of 50 mmol / L were added to a reaction kettle and stirred and mixed, then the pH value was adjusted to 6 with hydrochloric acid with a concentration of 4 mol / L, stirring was performed at 25 °C for 30 min, then 750 g of functionalized silica powder was added to the reaction kettle, the pH value was adjusted to 7.5 with sodium hydroxide solution with a concentration of 0.1 mol / L, and stirring was continued for 12 h, centrifugal filtration was performed, the filter cake was dispersed in 50 times the mass of hydrochloric acid with a molar concentration of 0.1 mol / L, stirring was performed at 30 °C for 10 h, centrifugal washing was performed for 5 times, the filter cake was vacuum dried to obtain sulfonated modified silica powder.

[0042] S3: 400 g of sulfonated modified silica powder, 400 g of antifungal agent IPBC, 16 L of deionized water and 4 L of anhydrous ethanol were added to a reaction kettle, stirring was performed at 1000 r / min for 15 min, ultrasonic dispersion was performed for 30 min, vacuum was drawn to -0.09 MPa, stirring was continued for 1.5 h, centrifugal filtration was performed, the filter cake was washed with anhydrous ethanol for 3 times, and vacuum drying was performed to obtain antifungal agent / nanosilica composite powder.

[0043] S4: 400 g of antifungal agent / nanosilica composite powder, 2.4 kg of zinc nitrate hexahydrate and 4 L of methanol aqueous solution with a mass fraction of 80% were added to a reaction kettle, stirring was performed at 500 r / min for 30 min, then 640 g of isophthalic acid, 1.32 kg of 3-amino-1,2,4-triazole and 4 L of N,N-dimethylformamide were added, stirring was continued for 10 min, stirring was performed at 115 °C for 75 h, centrifugal filtration was performed, the filter cake was washed with anhydrous methanol for 3 times, and vacuum drying was performed to obtain composite antifungal agent powder.

[0044] S5: 14 kg of one-component modified polysilicon epoxy resin, 10 kg of polysiloxane, 320 g of silane coupling agent KH550, 3.2 kg of water-based resin, 3.2 kg of cerium oxide powder, 12 kg of nano-titanium dioxide powder, 600 g of composite mildew-proof agent powder, 400 g of dispersing agent, 400 g of film-forming aid, 400 g of defoaming agent, 400 g of leveling agent, and 4 kg of water were stirred and mixed to obtain a high water-resistant wall coating.

[0045] Example 4: The present embodiment provides a high water-resistant wall coating, which is prepared by the following steps:

[0046] S1: 10 kg of monodisperse hollow nano-silica, 12 kg of (3-epoxypropoxy) propyl trimethoxysilane, and 150 L of anhydrous methanol were added to a reaction kettle and stirred and mixed, 10 kg of polyethyleneimine powder was then added to the reaction kettle, ultrasonic dispersion was performed for 40 min, and then stirring was performed at 70°C for 5-6 h, centrifugal filtration was performed, the filter cake was washed with anhydrous methanol for 5 times, and vacuum drying was performed to obtain functionalized silica powder.

[0047] S2: 1500 g of sodium m-carboxybenzenesulfonate, 900 g of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 900 g of N-hydroxysuccinimide, and 45 L of MES buffer solution with a concentration of 50 mmol / L were added to a reaction kettle and stirred and mixed, and then the pH value was adjusted to 6 with hydrochloric acid with a concentration of 4 mol / L, stirring was performed at 25°C for 30 min, 750 g of functionalized silica powder was then added to the reaction kettle, the pH value was adjusted to 7.5 with sodium hydroxide solution with a concentration of 0.1 mol / L, and stirring was continued for 12 h, centrifugal filtration was performed, the filter cake was dispersed in 50 times the mass of hydrochloric acid with a molar concentration of 0.1 mol / L, stirring was performed at 30°C for 10 h, centrifugal washing was performed for 5 times, the filter cake was vacuum dried to obtain sulfonated modified silica powder.

[0048] S3: 400 g of sulfonated modified silica powder, 400 g of mildew-proof agent IPBC, 16 L of deionized water, and 4 L of anhydrous ethanol were added to a reaction kettle, stirring was performed at 1000 r / min for 15 min, ultrasonic dispersion was performed for 30 min, vacuum was extracted to -0.09 MPa, stirring was continued for 1.5 h, centrifugal filtration was performed, the filter cake was washed with anhydrous ethanol for 3 times, and vacuum drying was performed to obtain a mildew-proof agent / nano-silica composite powder.

[0049] S4: 400 g of the antifungal agent / nano-silicon dioxide composite powder, 2.4 kg of zinc nitrate hexahydrate, and 4 L of a methanol aqueous solution with a mass fraction of 80% were added to a reaction kettle, stirred at 500 r / min for 30 min, then 640 g of isophthalic acid, 1.32 kg of 3-amino-1,2,4-triazole, and 4 L of N,N-dimethylformamide were added, and stirring was continued for 10 min, and then the reaction was carried out at 115°C for 75 h under stirring. The filter cake was washed with anhydrous methanol for 3 times, and vacuum dried to obtain the composite antifungal agent powder.

[0050] S5: 12 kg of the single-component modified polysilicon epoxy resin, 8 kg of polysiloxane, 80 g of silane coupling agent KH550, 2 kg of water-based resin, 2 kg of cerium oxide powder, 8 kg of nano-titanium dioxide powder, 200 g of the composite antifungal agent powder, 200 g of dispersant, 200 g of film-forming aid, 200 g of defoaming agent, 200 g of leveling agent, and 2 kg of water were stirred and mixed to obtain the high water-resistant wall coating.

[0051] The single-component modified polysilicon epoxy resin in the examples was purchased from Hubei Baisite Science and Technology Co., Ltd., with a brand of BS5188; the water-based resin was purchased from Nanjing Chuhai New Material Technology Co., Ltd., with a brand of MP50E; the dispersant was sodium dodecyl sulfonate; the film-forming aid was dodecanol ester, which was purchased from Shandong Jinyufeng New Material Co., Ltd.; the defoaming agent was BYK025, and the leveling agent was BYK333.

[0052] Comparative Example 1: On the basis of Example 3, without the treatment in steps S1 and S2, the single-dispersed hollow nano-silicon dioxide was directly used to replace the sulfonated modified silicon dioxide powder in step S3, and the subsequent steps remained unchanged to prepare the high water-resistant wall coating.

[0053] Comparative Example 2: On the basis of Example 3, without the treatment in step S4, and the remaining steps remained unchanged to prepare the high water-resistant wall coating.

[0054] Performance tests were carried out on Examples 1-4 and Comparative Examples 1-2. Different high water-resistant wall coatings were applied to the surface of cement boards, and the film thickness was kept consistent. After the paint film was dried and cured, different samples were obtained. The adhesion of the paint film of different samples was detected according to GB / T 9286-2021. The samples were respectively immersed in water at 23°C for 20 h, then frozen at-50°C for 2 h, and dried at 180°C for 2 h, and the cycle was repeated for 3 times. The surface of the sample after the cycle test was observed for phenomena such as powdering, cracking, blistering, peeling, etc. If there was no phenomenon, “normal” was filled. The mold resistance grade of the paint film before and after the cycle test was tested according to GB / T 1741-2020. The performance test results of the high water-resistant wall coating samples are shown in the following table:

[0055] Table 1 Performance test results of each high water-resistant wall coating sample

[0056]

[0057] As can be seen from Table 1, the paint films of the high water-resistant wall coatings in the examples and the comparative examples all have good adhesion and water resistance and cold-hot cycle resistance, but the samples in the examples have good mold resistance grades before and after the cycle test, the mold resistance grade in Comparative Example 1 becomes worse after the cycle test, the surface of the monodisperse hollow nanosilica that has not been modified by sulfonation cannot chelate zinc ions, and it is difficult to attach enough zinc nano metal organic framework on the surface, in combination with the analysis of Comparative Example 2, a layer of zinc nano metal organic framework is generated on the surface of the composite antifungal agent / nanosilica powder particles, which can reduce the migration rate of the antifungal agent IPBC, thereby improving the antifungal effect of the composite antifungal agent powder.

[0058] It should be noted that the relational terms herein such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any such actual relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0059] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and variations can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a highly water-resistant wall coating, characterized by, It comprises the following steps: The single-component modified polysilicon epoxy resin, polysiloxane, silane coupling agent KH550, water-based resin, cerium oxide powder, nano titanium dioxide powder, composite mildew-proof agent powder, dispersing agent, film-forming aid, defoaming agent, leveling agent and water are stirred and mixed to obtain a high water-resistant wall coating; The composite mildew-proof agent powder is prepared by the following steps: The mildew-proof agent / nano-silicon dioxide composite powder, zinc nitrate hexahydrate and 80wt% methanol aqueous solution are added into a reaction kettle, stirred at 300-500r / min for 20-30min, then isophthalic acid, 3-amino-1,2,4-triazole and N,N-dimethylformamide are added, continue to stir for 5-10min, and stir and react at 105-115℃ for 70-75h, centrifugal filtration, the filter cake is washed with anhydrous methanol for 2-3 times, and vacuum drying to obtain the composite mildew-proof agent powder. The mildew-proof agent / nano-silicon dioxide composite powder is prepared by the following steps: The polyethylene imine is modified on the surface of the monodisperse hollow nano-silicon dioxide to obtain functionalized silicon dioxide powder, then the carboxyl in m-caroxybenzenesulfonic acid sodium and the amino on the surface of the functionalized silicon dioxide powder are subjected to amidation reaction, and then the sulfonic acid sodium is converted into sulfonic acid group by using hydrochloric acid to obtain sulfonated modified silicon dioxide powder. The sulfonated modified silicon dioxide powder, mildew-proof agent IPBC, deionized water and anhydrous ethanol are added into a reaction kettle, stirred at 800-1000r / min for 10-15min, ultrasonic dispersion for 20-30min, vacuum extraction to-0.09MPa, continue to stir for 1-1.5h, centrifugal filtration, the filter cake is washed with anhydrous ethanol for 2-3 times, and vacuum drying to obtain the mildew-proof agent / nano-silicon dioxide composite powder.

2. The method for preparing a high water-resistant wall coating according to claim 1, characterized in that, The mass ratio of the single-component modified polysilicon epoxy resin, polysiloxane, silane coupling agent KH550, water-based resin, cerium oxide powder, nano titanium dioxide powder, composite mildew-proof agent powder, dispersing agent, film-forming aid, defoaming agent, leveling agent and water is 30-35:20-25:0.2-0.8:5-8:5-8:20-30:0.5-1.5:0.5-1:0.5-1:0.5-1:0.5-1:0.5-1:5-10.

3. The method for preparing a high water-resistant wall coating according to claim 1, characterized in that, The dosage ratio of the mildew-proof agent / nano-silicon dioxide composite powder, zinc nitrate hexahydrate, isophthalic acid, 3-amino-1,2,4-triazole, methanol aqueous solution and N,N-dimethylformamide is 1g:5-6g: 1.4-1.6g:3-3.3g:10mL:8-10mL.

4. The method for preparing a high water-resistant wall coating according to claim 1, characterized in that, The dosage ratio of the sulfonated modified silicon dioxide powder, mildew-proof agent IPBC, deionized water and anhydrous ethanol is 1g:0.8-1g:40mL:10mL.

5. The method of claim 1, wherein the high water-resistant wall coating is prepared by mixing the water-resistant base paint, the water-resistant additive, and the water-resistant pigment. 5 The sulfonated modified silicon dioxide powder is prepared by the following steps: Sodium m-carboxybenzenesulfonate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and MES buffer solution with a concentration of 50 mmol / L are added into a reaction kettle and stirred and mixed, then the pH value is adjusted to 5-6 by using hydrochloric acid with a concentration of 4 mol / L, stirring is carried out at 20-25℃ for 20-30 min, then functionalized silica powder is added, the pH value is adjusted to 7.5 by using sodium hydroxide solution with a concentration of 0.1 mol / L, and stirring is continued for 10-12 h, then centrifugal filtration is carried out, the filter cake is dispersed in 30-50 times the mass of hydrochloric acid with a concentration of 0.1 mol / L, stirring is carried out at 25-30℃ for 8-10 h, and the filter cake is washed by centrifugation for 3-5 times, then the filter cake is vacuum dried to obtain sulfonated modified silica powder.

6. The method of claim 5, wherein the high water-resistant wall coating is prepared by mixing the water-resistant base paint, the water-resistant additive, and the water-resistant pigment. The sodium m-carboxybenzenesulfonate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, MES buffer solution and functionalized silica powder are used in a ratio of 0.3-0.5 g: 0.2-0.3 g: 0.2-0.3 g: 10-15 mL: 0.15-0.25 g.

7. The method for preparing a highly water-resistant wall coating according to claim 1, characterized in that: The functionalized silica powder is prepared by the following steps: Monodisperse hollow nanosilica, (3-glycidoxypropyl) trimethoxysilane and anhydrous methanol are added into a reaction kettle and stirred and mixed, then polyethyleneimine powder is added into the reaction kettle, ultrasonic dispersion is carried out for 30-40 min, then stirring is carried out at 65-70℃ for 5-6 h, the filter cake is washed with anhydrous methanol for 3-5 times, and vacuum drying is carried out to obtain functionalized silica powder.

8. The method of claim 7, wherein the high water-resistant wall coating is prepared by mixing the water-resistant base paint, the water-resistant additive, and the water-resistant pigment, and then adding the water-resistant additive and the water-resistant pigment to the water-resistant base paint. The monodisperse hollow nanosilica, (3-glycidoxypropyl) trimethoxysilane, anhydrous methanol and polyethyleneimine powder are used in a ratio of 1 g: 1.1-1.2 g: 12-15 mL: 1 g.

9. A highly water resistant wall coating, characterized in that, The high water-resistant wall coating is prepared by the preparation method of any one of claims 1-8.

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