Two-component super-weather-resistant waterproof stone-like paint and preparation method thereof

Abstract

The application relates to a two-component super-weather-resistant waterproof stone-like paint and a preparation method thereof, and belongs to the technical field of new materials. The invention effectively improves the water resistance and aging resistance of the stone-like paint, and simultaneously increases the adhesion and moisture and heat resistance grade by introducing amphiphilic modified hydroxyethyl cellulose and modified high surface area kaolin in the first component and combining the joint action of the amino-silica aerogel in the second component.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of new materials, and particularly relates to a two-component super-weather-resistant waterproof imitation stone paint and a preparation method thereof. BACKGROUND

[0002] The imitation stone paint is a kind of coating with a decorative effect similar to natural stone, which is mainly prepared by using natural stone powder of different colors and water-based environmental protection materials, has natural color and good decorative effect, and has the characteristics of waterproofness and stain resistance, can effectively prevent the erosion of the building by the external harsh environment, and prolongs the service life of the building. With the rapid development of economic construction and the construction industry, the imitation stone paint has been widely applied in the external decoration construction due to its advantages of convenient construction, rich color and water-based environmental protection. With the universal application of the imitation stone paint in the construction field, the types of the imitation stone paint are more and more, and the characteristics are more and more obvious.

[0003] A kind of water-resistant and stain-resistant imitation stone paint and a preparation method thereof are disclosed in Chinese patent (publication number CN116285514A), which adds hydroxyl fullerene modified kaolinite. The hydroxyl fullerene can be spontaneously adsorbed on the hydroxyl surface of the kaolinite to increase more active sites, has a certain air purification effect, can enhance the impact resistance of the paint film as a filler, has good compatibility with the styrene-acrylic emulsion, and can improve the combination degree of other components in the system. By adding white corundum powder, the water washing resistance and stain resistance of the imitation stone paint can be improved. The modified styrene-acrylic emulsion has good permeability, can better match with other components, and ensures the combination degree of the paint system after the raw material components are compounded and mixed. However, the imitation stone paint disclosed in the patent has the following shortcomings and deficiencies: (1) poor water resistance, easy to cause blistering and peeling of the paint layer; (2) poor aging resistance during long-term use in the environment; (3) low adhesion grade and insufficient moisture resistance.

[0004] Therefore, it is an urgent problem to be solved in the industry to provide a two-component super-weather-resistant waterproof imitation stone paint, which effectively improves the water resistance and aging resistance by introducing a modified component, and increases the adhesion and moisture resistance grade. SUMMARY

[0005] In view of the above problems, the purpose of the present application is to provide a two-component super-weather-resistant waterproof imitation stone paint and a preparation method thereof. By introducing amphiphilic modified hydroxyethyl cellulose and modified kaolin with high specific surface area in the first component, and cooperating with the joint action of the amino-silica aerogel in the second component, the water resistance and aging resistance of the imitation stone paint are effectively improved, and the adhesion and moisture resistance grade are increased.

[0006] To achieve the above purpose, the present application provides the following technical solutions:

[0007] The first aspect of the present application provides a preparation method of a two-component super-weather-resistant waterproof imitation stone paint, comprising the following steps:

[0008] Step S1: 0.8-1.1 parts by weight of hydroxyethyl cellulose is added to 45-50 parts by weight of deionized water, dispersed at a speed of 800-1000 r / min for 20-30 min, then 0.2-0.4 parts by weight of polyvinyl alcohol, 0.1-0.2 parts by weight of palm wax and 25-35 parts by weight of filler are added, dispersed at a speed of 3200-3500 r / min for 40-60 min, then 25-35 parts by weight of styrene-acrylate emulsion, 1.2-1.5 parts by weight of lauryl alcohol ester, 0.9-1.2 parts by weight of propylene glycol and 0.1-0.2 parts by weight of isothiazolinone are added, and dispersed at a speed of 1200-1400 r / min for 10-20 min to obtain a first component A;

[0009] Step S2: 52-55 parts by weight of styrene-acrylate emulsion, 3-5 parts by weight of lauryl alcohol ester, 0.5-0.7 parts by weight of polycarbodiimide, 0.1-0.4 parts by weight of palm wax, 0.1-0.2 parts by weight of isothiazolinone, 1.2-1.5 parts by weight of bentonite and 10-20 parts by weight of silica aerogel are added to 45-50 parts by weight of deionized water, the temperature is controlled at 45-55℃, and dispersed at a speed of 900-1000 r / min for 40-60 min to obtain a second component B;

[0010] Step S3: 80-100 parts by weight of the first component A is dispersed at a speed of 400-450 r / min for 2-3 h, then 40-50 parts by weight of the second component B is added and dispersed at a speed of 150-180 r / min for 3-5 min to obtain a two-component super-weather-resistant waterproof imitation stone paint.

[0011] In some embodiments of the present application, the purity of the hydroxyethyl cellulose in step S1 is 95-96%, and the viscosity of a 1% mass concentration aqueous solution at 25℃ is 100-2000 mPa.s.

[0012] In some embodiments of the present application, the hydroxyethyl cellulose in step S1 is modified hydroxyethyl cellulose; the preparation method of the modified hydroxyethyl cellulose comprises: adding 20-25 parts by weight of hydroxyethyl cellulose into 100-120 parts by weight of deionized water, stirring for 1-2 h under a nitrogen atmosphere, adding 5-8 parts by weight of cerium ammonium nitrate and 10-15 parts by weight of methacryloyl ethyl sulfobetaine at 35-40℃, adjusting the pH to 7.2-7.4, and reacting for 4-6 h; after the reaction is completed, the product is separated by precipitation with acetone to obtain a precipitate; adding 35-40 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid and 10-15 parts by weight of sodium chloride into 200-220 parts by weight of deionized water, stirring for 0.5-0.8 h, then adjusting the pH to 7.2-7.4, adding 40-45 parts by weight of dimethyl diallyl ammonium chloride and 20-30 parts by weight of the aforementioned precipitate, and stirring for 1-2 h to obtain a mixed solution; transferring the mixed solution into a reaction kettle, placing it under a nitrogen atmosphere, adding 2-4 parts by weight of potassium persulfate at 80-85℃, and reacting for 6-8 h; drying and crushing to obtain the modified hydroxyethyl cellulose.

[0013] The modified hydroxyethyl cellulose contains a zwitterionic polymer, which contains both anionic groups and cationic groups on the molecular chain, can improve the wettability of the stone-like paint to the substrate by electrostatic interaction, makes the stone-like paint more easily spread uniformly on the surface of the substrate, forms a more close contact and penetrates into the micropores of the substrate, thereby strengthens the physical combination between the two, and thus improves the adhesion grade of the stone-like paint.

[0014] In some embodiments of the present application, the filler in step S1 is kaolin, and the particle size of the kaolin is 80-100 nm, and the specific surface area is 180-200 m 2 / g.

[0015] In some embodiments of the present application, the kaolin is modified kaolin; the preparation method of the modified kaolin comprises: calcining 100-120 parts by weight of kaolin at 800-820℃ for 2-4 h, cooling to room temperature, then impregnating with 250-300 parts by weight of a 20% sulfuric acid solution for 4-6 h, and then filtering, washing and drying to obtain acidified kaolin; adding 10-15 parts by weight of the acidified kaolin, 4-6 parts by weight of cetyltrimethylammonium bromide and 1-3 parts by weight of sodium hydroxide into 280-300 parts by weight of deionized water, stirring at 60-70℃ for 2-4 h, then transferring into a microwave reactor for microwave treatment, with a microwave output power of 800-1000 W, a temperature of 100-110℃ and a time of 1-2 h; after the microwave treatment is completed, cooling, filtering, washing and drying to obtain the modified kaolin.

[0016] The kaolin is treated by microwave and introduced with a quaternary ammonium salt cationic surface modifier to break the hydrogen bond between layers of the kaolin, increase the interlayer spacing of the kaolin, and thus increase the specific surface area. The high specific surface area of the modified kaolin can promote the paint layer of the stone-like paint to be more compact and smooth, reduce the penetration of moisture and other corrosive media, and improve the resistance of the stone-like paint to a humid and hot environment.

[0017] In some embodiments of the present application, the particle size of the silica aerogel in step S2 is 80-90 mu m.

[0018] In some embodiments of the present application, the silica aerogel is an aminated silica aerogel; the preparation method of the aminated silica aerogel comprises: adding 3-5 parts of gamma-aminopropyl triethoxysilane to 10-12 parts of anhydrous ethanol by weight and stirring for 1-3 hours, then adding 2-4 parts of deionized water and stirring for 10-12 hours of hydrolysis, adding 5-8 parts of tetraethyl orthosilicate after the hydrolysis is completed and stirring for 10-20 minutes, and then placing in a refrigeration room at-20 DEG C for gel treatment to obtain a silica wet gel; and the silica wet gel is sequentially subjected to aging treatment and supercritical drying treatment to obtain the aminated silica aerogel.

[0019] In some embodiments of the present application, the temperature of the aging treatment is 30-50 DEG C and the time is 1-2 hours; and the supercritical drying treatment is carbon dioxide supercritical drying treatment, the carbon dioxide pressure is 8-10 MPa, the drying temperature is 30-35 DEG C, and the drying time is 45-48 hours.

[0020] The aminated silica aerogel can react with the styrene-acrylic emulsion to improve the compactness between resin molecules in the styrene-acrylic emulsion, form a more solid network interconnection structure, obtain a barrier effect, reduce moisture penetration, and thus improve the water resistance of the stone-like paint.

[0021] In some embodiments of the present application, the alcoholysis degree of the polyvinyl alcohol is 87-89%;

[0022] In some embodiments of the present application, the melting point of the palm wax is 82-83 DEG C, the acid value is 2-7, and the saponification value is 78-89;

[0023] In some embodiments of the present application, the solid content of the styrene-acrylic emulsion is 47-49%, the particle size is 0.1-0.2 mu m, and the viscosity is 4000-8000 cps;

[0024] In some embodiments of the present application, the particle size of the bentonite is 5-10 mu m;

[0025] In some embodiments of the present application, the purity of the dodecanol ester is 99.3-99.6%, the purity of propylene glycol is 98-99%, the purity of isothiazolinone is 98-99%, and the purity of polycarbodiimide is 98-99%.

[0026] The second aspect of the present application provides a two-component super-weather-resistant waterproof imitation stone paint prepared by the method of the first aspect.

[0027] Compared with the prior art, the present application at least has the following technical effects: (1) the present application uses modified hydroxyethyl cellulose, modified kaolin and aminated silica aerogel to form a synergistic effect, the modified hydroxyethyl cellulose has a zwitterionic polymer, which contains both anionic groups and cationic groups on the molecular chain, so it can act as a bridge to connect the modified kaolin in the first component and the aminated silica aerogel in the second component, and form a three-dimensional network structure to enhance the stability of the imitation stone paint, improve its weather resistance and durability, and thus improve the aging resistance of the imitation stone paint; (2) the electrostatic effect generated by the zwitterionic polymer in the modified hydroxyethyl cellulose improves the physical bonding state of the imitation stone paint and the substrate, and improves the permeability of the imitation stone paint to the substrate, thereby reducing the risk of peeling and effectively increasing the adhesion; (3) the modified kaolin of the present application introduces quaternary ammonium salt cations and is treated by microwave, which destroys the hydrogen bonds between the layers of the kaolin, so that the kaolin has a high specific surface area, improves the compactness and smoothness of the paint layer of the imitation stone paint, reduces the influence of moisture or corrosive media, and thus enhances the moisture resistance of the imitation stone paint; (4) the present application modifies the silica aerogel by amination, and obtains a dense structure by the reaction of the amino groups with the molecules of the styrene-acrylic emulsion resin, which reduces the influence of moisture by the barrier effect and effectively improves the water resistance of the imitation stone paint. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 The product physical map of the two-component super-weather-resistant waterproof imitation stone paint of the present application. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical scheme and advantages of the present application more clear and obvious, the present application will be further described in detail. However, it should be understood that the description herein is only used to explain the present application and is not intended to limit the scope of the present application.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs, and the terms used herein in the specification are only for the purpose of describing specific embodiments and are not intended to limit the present application. The reagents and instruments used herein are commercially available, and the characterization means involved can be referred to the related description in the prior art, which will not be described herein.

[0031] The sources of some components in the examples and comparative examples are as follows:

[0032] Hydroxyethyl cellulose, product number HHR-250, purity 96%, viscosity of 1% mass concentration aqueous solution at 25°C 11200 mPa.s, purchased from Guangzhou Baiyu Biological Technology Co., Ltd.;

[0033] Polyvinyl alcohol, product number PA73430, alcoholysis degree 89%, purchased from Shanghai Chuang Sai Technology Co., Ltd.;

[0034] Palm wax, product number C104040, melting point 83°C, acid value 6, saponification value 82, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0035] Kaolin I, product number TG-Y-3, particle size 100 nm, specific surface area 200 m 2 / g, purchased from Guangzhou Changyu Chemical Co., Ltd.;

[0036] Kaolin II, product number 1332-58-7, particle size 300 nm, specific surface area 32 m 2 / g, purchased from Zaozhuang Sanxing New Material Co., Ltd., Shandong;

[0037] Styrene-acrylate emulsion, product number NaPoly 7199A, solid content 48%, particle size 0.2 μm, viscosity 4000 cps, purchased from Guangzhou Shuangpu Trading Chemical Co., Ltd.

[0038] Dodecanol ester, CAS number 25265-77-4, purity 99.5%, purchased from Shenzhen Longdi Chemical Co., Ltd.;

[0039] Propylene glycol, CAS number 57-55-6, purity 99%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0040] Isothiazolinone, CAS number 2682-20-4, purity 99%, purchased from Chongqing Ruiya Biological Technology Co., Ltd.;

[0041] Polycarbodiimide, CAS number 151-51-9, purity 99%, purchased from Hubei Tianmen Hengchang Chemical Co., Ltd.;

[0042] Bentonite, CAS number 1302-78-9, particle size 10 μm, purchased from Shijiazhuang Borui Building Material Co., Ltd.;

[0043] Silica aerogel, product number 091458, particle size 80 μm, purchased from Shanghai Cola Man Reagent Co., Ltd.;

[0044] Cerium ammonium nitrate, product number C3654, purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.;

[0045] Methacryloyl ethyl sulfobetaine, CAS No. 3637-26-1, purchased from Shanghai Aladdin Biochem Technology Co., Ltd.;

[0046] Acetone, CAS No. 67-64-1, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0047] 2-acrylamido-2-methylpropanesulfonic acid, CAS No. 15214-89-8, purchased from Shanghai Huayuan Century Trading Co., Ltd.;

[0048] Sodium chloride, CAS No. 7647-14-5, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0049] Dimethyldiallylammonium chloride, CAS No. 7398-69-8, purchased from Shanghai Aladdin Biochem Technology Co., Ltd.;

[0050] Potassium persulfate, CAS No. 7727-21-1, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0051] Sulfuric acid, CAS No. 7664-93-9, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0052] Cetyltrimethylammonium bromide, CAS No. 57-09-0; purchased from Shanghai Aladdin Biochem Technology Co., Ltd.;

[0053] Sodium hydroxide, CAS No. 1310-73-2, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0054] Gamma-aminopropyl triethoxysilane, product No. A17919, purchased from Beijing Inokai Technology Co., Ltd.;

[0055] Anhydrous ethanol, CAS No. 64-17-5, purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0056] Tetraethyl orthosilicate, product No. PA84187, purchased from Shanghai Creative Science and Technology Co., Ltd.

[0057] Example 1

[0058] The present embodiment provides a preparation method of a two-component super-weather-resistant waterproof stone-like paint, comprising the following steps:

[0059] Preparation of modified hydroxyethyl cellulose: 25 parts of hydroxyethyl cellulose was added into 120 parts of deionized water under stirring for 2 h under nitrogen atmosphere, 8 parts of cerium nitrate ammonium, 15 parts of methacryloyl ethyl sulfobetaine were added at 40℃, the pH was adjusted to 7.4, and the reaction was carried out for 6 h. After the reaction was completed, the product was separated by precipitation with acetone. 40 parts of 2-acrylamido-2-methylpropanesulfonic acid and 15 parts of sodium chloride were added into 220 parts of deionized water, stirred for 0.8 h, and then the pH was adjusted to 7.4. 45 parts of dimethyl diallyl ammonium chloride and 30 parts of the aforementioned precipitate were added, stirred for 2 h to obtain a mixed solution. The mixed solution was transferred to a reaction kettle, and 4 parts of potassium persulfate was added under nitrogen atmosphere at 85℃ for 8 h of reaction. After drying and crushing, the modified hydroxyethyl cellulose was obtained.

[0060] Preparation of modified kaolin: 120 parts of kaolin I (particle size 100 nm, specific surface area 200 m2 / g) was calcined at 820℃ for 4 h, and then cooled to room temperature. 300 parts of 20% sulfuric acid solution was added for impregnation for 6 h, and then filtered, washed and dried to obtain acidified kaolin. 15 parts of the acidified kaolin, 6 parts of cetyltrimethylammonium bromide and 3 parts of sodium hydroxide were added into 300 parts of deionized water, stirred at 70℃ for 4 h, and then transferred to a microwave reactor for microwave treatment. The microwave output power was 1000 W, the temperature was 110℃, and the time was 1 h. After microwave treatment, the product was cooled, filtered, washed and dried to obtain the modified kaolin.

[0061] Preparation of aminated silica aerogel: 5 parts of γ-aminopropyl triethoxysilane was added into 12 parts of anhydrous ethanol and stirred for 3 h. Then 4 parts of deionized water was added and stirred for 12 h for hydrolysis. After the hydrolysis was completed, 8 parts of tetraethyl orthosilicate was added and stirred for 20 min. Then the silica wet gel was treated by gelation in a refrigeration room at -20℃ to obtain the silica wet gel. The silica wet gel was subjected to aging treatment (temperature 50℃, time 1 h) and supercritical drying treatment (carbon dioxide supercritical drying treatment, carbon dioxide pressure 10 MPa, drying temperature 30℃, drying time 48 h) in sequence to obtain the aminated silica aerogel.

[0062] Step S1: 1.1 parts of modified hydroxyethyl cellulose was added into 50 parts of deionized water under a rotation speed of 1000 r / min for dispersion for 20 min. Then 0.4 parts of polyvinyl alcohol, 0.2 parts of palm wax and 35 parts of modified kaolin were added and dispersed at a rotation speed of 3500 r / min for 40 min. Then 35 parts of styrene-acrylate emulsion, 1.5 parts of lauryl ester, 1.2 parts of propylene glycol and 0.2 parts of isothiazolinone were added and dispersed at a rotation speed of 1400 r / min for 10 min to obtain a first component A.

[0063] Step S2: 55 parts of styrene-acrylic emulsion, 5 parts of dodecanol ester, 0.7 parts of polycarbodiimide, 0.4 parts of palm wax, 0.2 parts of isothiazolinone, 1.5 parts of bentonite and 20 parts of aminosilica aerogel were added into 50 parts of deionized water, the temperature was controlled at 55℃, and dispersed at a speed of 1000r / min for 40min to obtain the second component B;

[0064] Step S3: 100 parts of the first component A was dispersed at a speed of 450r / min for 2h, then 50 parts of the second component B was added and dispersed at a speed of 180r / min for 3min to obtain the two-component super-weather-resistant waterproof stone-like paint.

[0065] Example 2

[0066] The present embodiment provides a preparation method of a two-component super-weather-resistant waterproof stone-like paint, comprising the following steps:

[0067] Preparation of modified hydroxyethyl cellulose: 20 parts of hydroxyethyl cellulose was added into 100 parts of deionized water and stirred for 1h under nitrogen atmosphere, 5 parts of cerium nitrate ammonium, 10 parts of methacryloyl ethyl sulfobetaine were added at 35℃, the pH was adjusted to 7.2, and the reaction was carried out for 4h, then the reaction was completed and separated by precipitation with acetone to obtain the precipitate; 35 parts of 2-acrylamido-2-methylpropanesulfonic acid and 10 parts of sodium chloride were added into 200 parts of deionized water and stirred for 0.5h, then the pH was adjusted to 7.2, 40 parts of dimethyl diallyl ammonium chloride and 20 parts of the aforementioned precipitate were added, and stirred for 1h to obtain a mixed solution, the mixed solution was transferred to a reaction kettle, and placed under nitrogen atmosphere, 2 parts of potassium persulfate was added at 80℃ and reacted for 6h, dried, and crushed to obtain modified hydroxyethyl cellulose.

[0068] Preparation of modified kaolin: 100 parts of kaolin I was calcined at 800℃ for 2h, cooled to room temperature, then impregnated with 250 parts of 20% mass concentration sulfuric acid solution for 4h, then filtered, washed and dried to obtain acidified kaolin; 10 parts of the acidified kaolin, 4 parts of cetyltrimethylammonium bromide and 1 part of sodium hydroxide were added into 280 parts of deionized water, stirred at 60℃ for 2h, then transferred to a microwave reactor for microwave treatment, the microwave output power was 800W, the temperature was 100℃, and the time was 1h, after microwave treatment, the mixture was cooled, filtered, washed and dried to obtain the modified kaolin.

[0069] Preparation of aminosilica aerogel: 3 parts of γ-aminopropyl triethoxysilane were added into 10 parts of anhydrous ethanol and stirred for 1 h, then 2 parts of deionized water were added and hydrolyzed for 10 h, after the hydrolysis was completed, 5 parts of tetraethyl orthosilicate were added and stirred for 10 min, then the silica wet gel was obtained by gel treatment in a refrigeration room at-20 DEG C; the silica wet gel was subjected to aging treatment (temperature was 30 DEG C, time was 2 h) and supercritical drying treatment (carbon dioxide supercritical drying treatment, carbon dioxide pressure was 8 MPa, drying temperature was 30 DEG C, drying time was 48 h) in sequence, and aminosilica aerogel was obtained.

[0070] Step S1: 0.8 parts of modified hydroxyethyl cellulose were added into 45 parts of deionized water, and dispersed at a rotation speed of 800 r / min for 30 min, then 0.2 parts of polyvinyl alcohol, 0.1 parts of palm wax and 25 parts of modified kaolin were added, and dispersed at a rotation speed of 3200 r / min for 60 min, then 25 parts of styrene-acrylate emulsion, 1.2 parts of lauryl alcohol ester, 0.9 parts of propylene glycol and 0.1 parts of isothiazolinone were added, and dispersed at a rotation speed of 1200 r / min for 20 min, to obtain a first component A;

[0071] Step S2: 52 parts of styrene-acrylate emulsion, 3 parts of lauryl alcohol ester, 0.5 parts of polycarbodiimide, 0.1 parts of palm wax, 0.1 parts of isothiazolinone, 1.2 parts of bentonite and 10 parts of aminosilica aerogel were added into 45 parts of deionized water, and dispersed at a rotation speed of 900 r / min for 60 min, while the temperature was controlled at 45 DEG C, to obtain a second component B;

[0072] Step S3: 800 parts of the first component A were dispersed at a rotation speed of 400 r / min for 3 h, then 40 parts of the second component B were added and dispersed at a rotation speed of 150 r / min for 5 min, to obtain a two-component super-weather-resistant waterproof stone-like paint.

[0073] Example 3

[0074] The embodiment provides a preparation method of a two-component super-weather-resistant waterproof stone-like paint, comprising the following steps:

[0075] Preparation of modified hydroxyethyl cellulose: 24 parts of hydroxyethyl cellulose were added to 110 parts of deionized water under stirring for 1 h under a nitrogen atmosphere, 6 parts of cerium nitrate and 12 parts of methacryloyl ethyl sulfobetaine were added at 35℃, the pH was adjusted to 7.3, and the reaction was carried out for 5 h. After the reaction was completed, the product was separated by precipitation with acetone. 38 parts of 2-acrylamido-2-methylpropanesulfonic acid and 12 parts of sodium chloride were added to 210 parts of deionized water, stirred for 0.6 h, and then the pH was adjusted to 7.3. 42 parts of dimethyl diallyl ammonium chloride and 28 parts of the aforementioned precipitate were added, stirred for 1 h to obtain a mixed solution, which was transferred to a reaction kettle and placed under a nitrogen atmosphere. 3 parts of potassium persulfate was added at 82℃ and the reaction was carried out for 7 h. After drying and crushing, the modified hydroxyethyl cellulose was obtained.

[0076] Preparation of modified kaolin: 110 parts of kaolin I were calcined at 810℃ for 3 h, cooled to room temperature, and then impregnated with 280 parts of a 20% mass fraction sulfuric acid solution for 5 h. After filtration, washing, and drying, the acidified kaolin was obtained. 12 parts of the acidified kaolin, 5 parts of cetyltrimethylammonium bromide, and 2 parts of sodium hydroxide were added to 290 parts of deionized water, stirred at 68℃ for 3 h, and then transferred to a microwave reactor for microwave treatment. The microwave output power was 900 W, the temperature was 105℃, and the time was 2 h. After microwave treatment, cooling, filtration, washing, and drying, the modified kaolin was obtained.

[0077] Preparation of aminated silica aerogel: 4 parts of γ-aminopropyl triethoxysilane were added to 11 parts of anhydrous ethanol and stirred for 2 h. Then 3 parts of deionized water was added and stirred for 11 h for hydrolysis. After the hydrolysis was completed, 6 parts of tetraethyl orthosilicate was added and stirred for 15 min. Then the silica wet gel was treated with gelation in a refrigeration room at -20℃ to obtain a silica wet gel. The silica wet gel was subjected to aging treatment (temperature 40℃, time 2 h) and supercritical drying treatment (carbon dioxide supercritical drying treatment, carbon dioxide pressure 9 MPa, drying temperature 32℃, drying time 46 h) in sequence to obtain the aminated silica aerogel.

[0078] Step S1: 0.9 parts of modified hydroxyethyl cellulose were added to 48 parts of deionized water under a rotation speed of 900 r / min for dispersion for 25 min. Then 0.3 parts of polyvinyl alcohol, 0.2 parts of palm wax, and 30 parts of modified kaolin were added and dispersed at a rotation speed of 3300 r / min for 50 min. Then 30 parts of a styrene-acrylic emulsion, 1.4 parts of lauryl alcohol ester, 1.1 parts of propylene glycol, and 0.2 parts of isothiazolinone were added and dispersed at a rotation speed of 1300 r / min for 15 min to obtain a first component A.

[0079] Step S2: 54 parts of styrene-acrylic emulsion, 4 parts of lauryl alcohol ester, 0.6 parts of polycarbodiimide, 0.2 parts of palm wax, 0.2 parts of isothiazolinone, 1.4 parts of bentonite and 15 parts of aminosilica aerogel were added into 48 parts of deionized water, the temperature was controlled at 48℃, and dispersed at a speed of 950r / min for 50min to obtain the second component B;

[0080] Step S3: 90 parts of the first component A were dispersed at a speed of 420r / min for 3h, then 46 parts of the second component B were added and dispersed at a speed of 160r / min for 4min to obtain the two-component super-weather-resistant waterproof stone-like paint.

[0081] Comparative Example 1

[0082] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose, the commercially available kaolin I is used instead of the modified kaolin, and the commercially available silica aerogel is used instead of the aminosilica aerogel.

[0083] Comparative Example 2

[0084] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that the commercially available kaolin I is used instead of the modified kaolin, and the commercially available silica aerogel is used instead of the aminosilica aerogel.

[0085] Comparative Example 3

[0086] This comparative example provides a preparation method of stone-like paint, which is different from Comparative Example 2 in that the amount of modified hydroxyethyl cellulose is changed from 1.1 parts to 0.4 parts.

[0087] Comparative Example 4

[0088] This comparative example provides a preparation method of stone-like paint, which is different from Comparative Example 2 in that the amount of modified hydroxyethyl cellulose is changed from 1.1 parts to 2.2 parts.

[0089] Comparative Example 5

[0090] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose, and the commercially available silica aerogel is used instead of the aminosilica aerogel.

[0091] Comparative Example 6

[0092] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose, and the commercially available kaolin I is used instead of the modified kaolin.

[0093] Comparative Example 7

[0094] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that a commercially available hydroxyethyl cellulose is used instead of modified hydroxyethyl cellulose.

[0095] Comparative Example 8

[0096] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that a commercially available kaolin I is used instead of modified kaolin.

[0097] Comparative Example 9

[0098] This comparative example provides a preparation method of stone-like paint, which is different from Example 1 in that a commercially available silica aerogel is used instead of aminosilica aerogel.

[0099] Comparative Example 10

[0100] This comparative example provides a preparation method of stone-like paint, which is different from Comparative Example 5 in that a commercially available kaolin II (specific surface area 32 m 2 / g) is used instead of commercially available kaolin I (specific surface area 200 m 2 / g) to prepare modified kaolin.

[0101] The stone-like paints prepared in the above examples and comparative examples are subjected to the following tests:

[0102] Water resistance test: The test is carried out in accordance with the requirements of GB / T 1733-1993 Paint Film Resistance to Water Test.

[0103] Aging resistance test: The test is carried out in accordance with the requirements of GB / T 1865-2009 Color Paint and Varnish Artificial Climate Aging and Artificial Radiation Exposure Filtered Xenon Arc Radiation.

[0104] Adhesion test: The test is carried out in accordance with the requirements of GB / T 1720-2020 Paint Film Scratch Test.

[0105] Wet heat resistance test: The test is carried out in accordance with the requirements of GB / T 1740-2007 Paint Film Resistance to Wet Heat Test.

[0106] The performance test results are shown in Table 1:

[0107] Table 1 Performance Test Results

[0108]

[0109]

[0110] From the performance test results, it can be seen that the effect of Examples 1-3 is good, the water resistance is >100h, the aging resistance is >45 days, the adhesion is grade 2, and the wet heat resistance is grade 1; this is because the present application introduces the amphiphilic modified hydroxyethyl cellulose and the modified high surface area kaolin in the first component, and cooperates with the amino-silica aerogel in the second component, which effectively improves the water resistance and aging resistance of the stone-like paint, and increases the adhesion and the wet heat resistance.

[0111] Compared with Example 1, the water resistance, aging resistance, adhesion and wet heat resistance of Comparative Example 1 are all reduced, because the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose, the commercially available kaolin I is used instead of the modified kaolin, and the commercially available silica aerogel is used instead of the amino-silica aerogel. Compared with Example 1, the water resistance, aging resistance and wet heat resistance of Comparative Example 2 are all reduced, because the commercially available kaolin I is used instead of the modified kaolin, and the commercially available silica aerogel is used instead of the amino-silica aerogel. Compared with Comparative Example 2, the adhesion of Comparative Example 3 is reduced, because the amount of the modified hydroxyethyl cellulose is changed from 1.1 parts to 0.4 parts, and the electrostatic effect is not strong enough to cause a weak physical combination. Compared with Comparative Example 2, the adhesion of Comparative Example 4 is reduced, because the amount of the modified hydroxyethyl cellulose is changed from 1.1 parts to 2.2 parts, and the electrostatic effect is too strong to affect the formability of the stone-like paint. Comparative Example 5 is not formed and cannot be tested, because the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose, and the commercially available silica aerogel is used instead of the amino-silica aerogel. Compared with Example 1, the water resistance, aging resistance and adhesion of Comparative Example 6 are all reduced, because the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose, and the commercially available kaolin I is used instead of the modified kaolin. Compared with Example 1, the aging resistance and adhesion of Comparative Example 7 are reduced, because the commercially available hydroxyethyl cellulose is used instead of the modified hydroxyethyl cellulose. Compared with Example 1, the aging resistance and wet heat resistance of Comparative Example 8 are reduced, because the commercially available kaolin I is used instead of the modified kaolin. Compared with Example 1, the water resistance and aging resistance of Comparative Example 9 are reduced, because the commercially available silica aerogel is used instead of the amino-silica aerogel. Compared with Comparative Example 5, the wet heat resistance is reduced, because the commercially available kaolin II (with a specific surface area of 32 m 2 / g) is used instead of the commercially available kaolin I (with a specific surface area of 200 m 2 / g) to prepare the modified kaolin, and the specific surface area of the commercially available kaolin II is small, so the modification effect is not good, and the wet heat resistance is reduced.

[0112] The applicant declares that the present application is illustrated by the above-mentioned embodiments, but the present application is not limited to the above-mentioned embodiments, that is, the present application does not mean that the present application must rely on the above-mentioned embodiments to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

[0113] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above-mentioned embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

[0114] In addition, it should be noted that each specific technical feature described in the above-mentioned specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combination manners.

Claims

1. A method for preparing a two-component, ultra-weather-resistant, waterproof, stone-like paint, characterized in that, Includes the following steps: Step S1: By weight, add 0.8-1.1 parts of hydroxyethyl cellulose to 45-50 parts of deionized water and disperse at 800-1000 r / min for 20-30 min. Add 0.2-0.4 parts of polyvinyl alcohol, 0.1-0.2 parts of palm wax and 25-35 parts of filler and disperse at 3200-3500 r / min for 40-60 min. Then add 25-35 parts of styrene-acrylic emulsion, 1.2-1.5 parts of dodecyl alcohol ester, 0.9-1.2 parts of propylene glycol and 0.1-0.2 parts of isothiazolinone and disperse at 1200-1400 r / min for 10-20 min to obtain the first component A. The modified hydroxyethyl cellulose is prepared by adding 20-25 parts by weight of hydroxyethyl cellulose to 100-120 parts of deionized water, stirring under a nitrogen atmosphere for 1-2 hours, adding 5-8 parts of cerium ammonium nitrate and 10-15 parts of methacryloyl ethyl sulfobetaine at 35-40°C, adjusting the pH to 7.2-7.4, reacting for 4-6 hours, and then separating the precipitate with acetone after the reaction to obtain the precipitate; then adding 35-40 parts of 2-acrylamide... 2-methylpropanesulfonic acid and 10-15 parts of sodium chloride were added to 200-220 parts of deionized water and stirred for 0.5-0.8 hours. The pH was adjusted to 7.2-7.

4. 40-45 parts of dimethyldiallylammonium chloride and 20-30 parts of the aforementioned precipitate were added and stirred for 1-2 hours to obtain a mixture. The mixture was transferred to a reaction vessel and placed under a nitrogen atmosphere. 2-4 parts of potassium persulfate were added at 80-85°C and reacted for 6-8 hours. The mixture was dried, pulverized, and modified hydroxyethyl cellulose was obtained. The filler has a particle size of 80–100 nm and a specific surface area of ​​180–200 m². 2 The modified kaolin is prepared by the following method: 100-120 parts by weight of kaolin are calcined at 800-820℃ for 2-4 hours, cooled to room temperature, and then impregnated with 250-300 parts by weight of 20% sulfuric acid solution for 4-6 hours. After filtration, washing, and drying, acidified kaolin is obtained. 10-15 parts of the acidified kaolin, 4-6 parts of hexadecyltrimethylammonium bromide, and 1-3 parts of sodium hydroxide are added to 280-300 parts of deionized water and stirred at 60-70℃ for 2-4 hours. The mixture is then transferred to a microwave reactor for microwave treatment at a microwave output power of 800-1000W, a temperature of 100-110℃, and a time of 1-2 hours. After microwave treatment, the mixture is cooled, filtered, washed, and dried to obtain modified kaolin. Step S2: By weight, add 52-55 parts of styrene-acrylic emulsion, 3-5 parts of dodecyl alcohol ester, 0.5-0.7 parts of polycarbodiimide, 0.1-0.4 parts of palm wax, 0.1-0.2 parts of isothiazolinone, 1.2-1.5 parts of bentonite and 10-20 parts of silica aerogel to 45-50 parts of deionized water, control the temperature at 45-55℃, and disperse at a speed of 900-1000 r / min for 40-60 min to obtain the second component B; The silica aerogel is an aminated silica aerogel, and its preparation method includes: adding 3-5 parts by weight of γ-aminopropyltriethoxysilane to 10-12 parts by weight of anhydrous ethanol and stirring for 1-3 hours; adding 2-4 parts by weight of deionized water and stirring for hydrolysis for 10-12 hours; after hydrolysis, adding 5-8 parts by weight of tetraethyl orthosilicate and stirring for 10-20 minutes; and placing the mixture in a freezer at -20°C for gelation treatment to obtain a wet silica gel; and subjecting the wet silica gel to aging treatment and supercritical drying treatment in sequence to obtain an aminated silica aerogel. Step S3: By weight, disperse 80-100 parts of the first component A at a speed of 400-450 r / min for 2-3 hours, add 40-50 parts of the second component B, and disperse at a speed of 150-180 r / min for 3-5 minutes to obtain a two-component super weather-resistant waterproof imitation stone paint.

2. The preparation method of a two-component ultra-weather-resistant waterproof imitation stone paint according to claim 1, characterized in that, The hydroxyethyl cellulose mentioned in step S1 has a purity of 95-96%, and the viscosity of a 1% aqueous solution at 25°C is 100-2000 mPa·s.

3. The preparation method of a two-component ultra-weather-resistant waterproof imitation stone paint according to claim 1, characterized in that, The particle size of the silica aerogel in step S2 is 80-90 μm.

4. The preparation method of a two-component ultra-weather-resistant waterproof imitation stone paint according to claim 3, characterized in that, The aging treatment is performed at a temperature of 30–50°C for 1–2 hours; the supercritical drying treatment is a carbon dioxide supercritical drying treatment with a carbon dioxide pressure of 8–10 MPa, a drying temperature of 30–35°C, and a drying time of 45–48 hours.

5. The preparation method of a two-component ultra-weather-resistant waterproof imitation stone paint according to claim 1, characterized in that, The degree of alcoholysis of the polyvinyl alcohol is 87-89%; The palm wax has a melting point of 82-83°C, an acid value of 2-7, and a saponification value of 78-89. The styrene-acrylic emulsion has a solid content of 47-49%, a particle size of 0.1-0.2 μm, and a viscosity of 4000-8000 cps; The bentonite has a particle size of 5–10 μm; The purity of the dodecyl alcohol ester is 99.3-99.6%, the purity of propylene glycol is 98-99%, the purity of isothiazolinone is 98-99%, and the purity of polycarbodiimide is 98-99%.

6. A two-component, ultra-weather-resistant, waterproof, stone-like paint, characterized in that, Prepared by the method according to any one of claims 1 to 5.

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