CN117683450A - Water-based nano waterproof coating and preparation method and application thereof - Google Patents
Water-based nano waterproof coating and preparation method and application thereof Download PDFInfo
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- CN117683450A CN117683450A CN202410155357.0A CN202410155357A CN117683450A CN 117683450 A CN117683450 A CN 117683450A CN 202410155357 A CN202410155357 A CN 202410155357A CN 117683450 A CN117683450 A CN 117683450A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 44
- 239000001913 cellulose Substances 0.000 claims abstract description 44
- 239000002159 nanocrystal Substances 0.000 claims abstract description 31
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- 239000005018 casein Substances 0.000 claims abstract description 29
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000021240 caseins Nutrition 0.000 claims abstract description 29
- 239000003973 paint Substances 0.000 claims abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920000875 Dissolving pulp Polymers 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000010426 asphalt Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
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- 238000011161 development Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
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- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000020289 caffè mocha Nutrition 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of waterproof paint, in particular to a water-based nano waterproof paint, a preparation method and application thereof, wherein the water-based nano waterproof paint comprises the following material components in parts by weight: 90 parts of polyurethane; 5 parts of modified cellulose nanocrystalline; 3 parts of nano titanium dioxide; 25 parts of casein solution; 3 parts of graphene; 1.5 parts of film forming additive. According to the water-based nano waterproof coating, the preparation method and the application thereof, polyethylene glycol is grafted to the surface of cellulose nanocrystals to obtain polyethylene glycol grafted modified cellulose nanocrystals, and modified cellulose nanocrystals and casein solution are introduced into polyurethane, so that the comprehensive properties of the film forming agent, such as extensibility, flexibility resistance and the like, are improved, the tensile property of the coating is improved, the elongation at break is increased, the corrosion resistance is improved, and the adhesive property is good and the toughness is strong.
Description
Technical Field
The invention relates to the field of waterproof paint, in particular to a water-based nano waterproof paint, a preparation method and application thereof.
Background
Along with the enhancement of environmental protection consciousness, the water-based paint becomes a popular product in the market, the development and application of the waterproof paint begin in the 60 s, and various chemical industry offcuts are taken as raw materials to develop the product in the early stage, and the development is stopped due to unstable quality and performance. In the same time, a great deal of work has been done on improving the water-resistant paint formulation of petroleum asphalt with high polymers. The neoprene-asphalt waterproof paint appears in the middle of 60 s, the reclaimed rubber-asphalt waterproof paint appears in the early of 70 s, and the engineering application is successful. With the stable development of the synthetic polymer material industry, waterproof coatings developed by taking various high-quality synthetic rubbers and synthetic resins as raw materials are put into use successively in the 80 s: such as bi-component polyurethane waterproof paint, acrylic acid ester light-colored waterproof paint, cationic neoprene latex asphalt waterproof paint, silicone rubber waterproof paint and the like, and rubber asphalt waterproof paint and synthetic polymer waterproof paint are occupying larger and larger proportion in the waterproof engineering application of China. The petroleum asphalt is used as the main material, and the polymer is used for modification, so that the petroleum asphalt has a long history, has wide raw material sources and low cost, and is suitable for general waterproof engineering with large amount of surface light; the paint mainly made of synthetic polymer materials has better performance but higher price; the wall cracks to cause the surface cracking of the paint due to the deformation of the building, and the waterproof effect is reduced. Therefore, asphalt waterproof coatings are used less and less, and polyurethane waterproof coatings are valued for the advantages of excellent elasticity, durability, light waterproof layer, convenient construction and maintenance, easy component adjustment, capability of being used for different parts of a building, good integrity and the like.
At present, polyurethane waterproof paint has poor overall performance and unstable quality. The single-component polyurethane waterproof paint is easy to cause long curing time and delay construction period due to insufficient humidity in the air. In the two-component polyurethane waterproof paint, MOCA (3, 3-dichloro-4, 4-diaminodiphenylmethane, commonly called Mocha) which is suspected to be a cancerogenic substance for human bodies is often used as a curing agent, and contains a large amount of volatile organic solvents (such as toluene, xylene, coumarone resin and the like), and the two-component polyurethane paint is difficult to stabilize due to the fact that the components of materials are complex, and the two-component polyurethane paint is limited by site conditions when in use; although the aqueous polyurethane coating accords with the development trend, the hydrophilic groups are introduced into the molecules, so that the coating film has poor water resistance and chemical resistance and is especially unsuitable for a long-term water immersion environment.
Disclosure of Invention
Based on the water-based nano waterproof coating and the preparation method thereof, the invention provides a water-based nano waterproof coating and solves the problems of poor water resistance and chemical resistance of the existing single water-based waterproof coating.
According to a first aspect of the invention, there is provided an aqueous nano waterproof coating comprising the following material components in parts by weight:
90 parts of polyurethane;
5 parts of modified cellulose nanocrystalline;
3 parts of nano titanium dioxide;
25 parts of casein solution;
3 parts of graphene;
1.5 parts of film forming additive.
According to the embodiment of the invention, the modified cellulose nanocrystalline is cellulose nanocrystalline grafted and modified by polyethylene glycol.
According to an embodiment of the present invention, the mass ratio of the polyethylene glycol to the cellulose nanocrystal is (1-2): 10.
according to the embodiment of the invention, the surface of the nano titanium dioxide is coated with aluminum hydroxide.
According to an embodiment of the invention, the film forming auxiliary agent comprises a composition of diatomite, silica gel and triethylene glycol monomethyl ether, wherein the mass ratio of the diatomite to the silica gel to the triethylene glycol monomethyl ether is 49:100:1.
the film forming auxiliary agent can avoid agglomeration, is favorable for forming a film of the coating and improves the antirust effect of the coating.
According to the embodiment of the invention, the casein solution comprises an aqueous solution of casein, and the mass fraction of the casein to water is 1: (9-10).
According to a second aspect of the present invention, there is provided a method for preparing an aqueous nano waterproof coating material, comprising the steps of:
step 1, preparing modified cellulose nanocrystals;
step 2, blending polyurethane, casein solution and modified cellulose nanocrystalline in a solvent to obtain a component A;
step 3, mixing nano titanium dioxide, graphene and a film forming auxiliary agent in a solvent to obtain a component B;
and step 4, mixing the component A and the component B, and regulating the viscosity to obtain the water-based nano waterproof coating.
According to an embodiment of the present invention, the method of modifying cellulose nanocrystals includes:
step 1, dissolving cellulose nanocrystalline powder in water to form a dissolving solution;
step 2, dropwise adding an alkaline solution into the dissolution solution, and stirring for 20-40min;
and step 3, adding the small molecular weight polyethylene glycol into the dissolution liquid, heating at 60-70 ℃, and stirring for 6-8h to obtain the modified cellulose nanocrystalline.
According to an embodiment of the invention, a mixed solvent comprising acetone and ethyl acetate in a mass ratio of 1:1 is used for adjusting the viscosity.
According to a third aspect of the invention, there is provided the use of an aqueous nano-waterproof coating for walls and metal surfaces.
According to the technical scheme, the water-based nano waterproof coating provided by the invention and the preparation method and application thereof have the following beneficial effects:
according to the water-based nano waterproof coating and the preparation method and application thereof, polyethylene glycol is grafted to the surface of cellulose nanocrystals in an alkaline solution to obtain polyethylene glycol grafted modified cellulose nanocrystals, the modified cellulose nanocrystals are introduced into polyurethane, so that the crystallization activation energy of the polyurethane is reduced, the crystallization temperature of the polyurethane is reduced, the crystallization nucleation of the polyurethane is promoted, the polyethylene glycol is grafted to the cellulose nanocrystals, the compatibility of the cellulose nanocrystals and the polyurethane can be effectively improved, and the interaction between molecular chains is enhanced, so that the strength of the cellulose nanocrystals is enhanced.
The casein solution is mixed with the modified cellulose nanocrystals and polyurethane, so that the casein solution reacts with hydrophilic groups such as amino groups, carboxyl groups and hydroxyl groups in the modified cellulose nanocrystals and the polyurethane, the water resistance and wet rubbing resistance of the coating are improved, and the polyurethane can block polar groups among casein molecular chains to form hydrogen bonds, so that the comprehensive properties such as extensibility and bending resistance of the film forming agent are improved, interaction between the casein and the modified cellulose nanocrystals is improved, the tensile property of the coating is improved, the elongation at break is increased, the corrosion resistance is improved, and the adhesive property is good and the toughness is strong.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The following detailed description of the technical scheme of the present invention is given by way of preferred examples, which are given by way of illustration only and not limitation, and the specific preparation methods are as follows.
Example 1: the water-based nano waterproof coating comprises the following material components in parts by weight:
90g of polyurethane;
5g of modified cellulose nanocrystalline;
3g of nano titanium dioxide;
25g of casein solution;
3g of graphene;
1.5g of film forming auxiliary agent.
The mass ratio of polyethylene glycol to cellulose nanocrystalline is 1:10.
the casein solution comprises an aqueous solution of casein, and the mass fraction of the casein to water is 1:9.
the film forming auxiliary agent comprises 0.49g of diatomite, 1g of silica gel and 0.01g of triethylene glycol monomethyl ether, and finally sample 1 is obtained.
Step 1, dissolving cellulose nanocrystalline powder in water to form a dissolving solution;
step 2, dropwise adding the alkaline solution into the dissolution solution, and stirring for 30min;
step 3, adding small molecular weight polyethylene glycol into the dissolution liquid, heating at 65 ℃, and stirring for 7 hours to obtain modified cellulose nanocrystalline;
step 4, blending polyurethane, casein solution and modified cellulose nanocrystalline in a solvent to obtain a component A;
step 5, mixing the nano titanium dioxide, the graphene and the film forming auxiliary agent in a solvent to obtain a component B;
and 6, mixing the component A and the component B, and adopting a mixed solvent comprising acetone and ethyl acetate in a mass ratio of 1:1 to adjust viscosity to obtain the water-based nano waterproof coating.
Example 2: the preparation method is the same as in example 1, except that the mass ratio of polyethylene glycol to cellulose nanocrystals is 2:10.
example 3: the preparation method is the same as in example 1, except that the casein solution comprises an aqueous solution of casein, and the mass fraction of casein to water is 1:10.
example 4: the preparation method was the same as in example 1, except that 3g of nano titanium dioxide coated with aluminum hydroxide was used.
Comparative example 1: the preparation method was the same as in example 1, except that cellulose nanocrystals were used.
Comparative example 2: the preparation method is the same as in example 1, except that casein solution is not included.
According to the embodiment of the present invention, preservatives, dispersants, defoamers, pigments and the like may be further added, and additives conventionally used in water-based paints may be employed, which are not specified in detail in the present invention.
Experimental example: the physical properties of the waterproof coatings prepared in examples 1-4 and comparative examples 1-2 are tested, a proper amount of the waterproof coatings prepared in examples 1-4 and comparative examples 1-2 are cured at normal temperature to prepare a coating film, the cured material with the thickness of 1.5+/-0.2 mm is ensured to detect each property of the coating according to the standard index of the building material industry of the people's republic of China, and the detection result shows that each conventional property index of the coating meets the national standard requirement.
Table 1 table of performance tests for examples 1-4 and comparative examples 1-2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Appearance of | Leveling, uniformity and smoothness | Leveling, uniformity and smoothness | Leveling, uniformity and smoothness | Leveling, uniformity and smoothness | With agglomerations | Leveling, uniformity and smoothness |
| Water resistance | 96h+ | 96h+ | 96h+ | 96h+ | 90h | 96h+ |
| Toughness mm | 1 | 1 | 1 | - | 0 | 0 |
| Salt spray resistance h | 1000+ | 1000+ | 1000+ | 1000+ | 720 | 540 |
| Tensile strength MPa | 690 | 680 | 690 | 670 | 560 | 540 |
| Distilled water soaking for 7 days, weight gain% | 0.26 | 0.35 | 0.28 | 0.31 | 2.21 | 1.36 |
| 3.5% sodium chloride for 7 days, weight gain% | 0.41 | 0.49 | 0.38 | 0.42 | 2.38 | 1.98 |
| Elongation at break% | 660 | 670 | 690 | 680 | 540 | 580 |
| Low temperature flexibility of-35 DEG C | No crack | No crack | No crack | No crack | No crack | With cracks |
As can be seen from the contents in Table 1, examples 1 to 4 have relatively good properties in each test, are effective in corrosion resistance, and have relatively good mechanical properties. From this, it can be seen that polyethylene glycol is grafted to the surface of cellulose nanocrystals to obtain polyethylene glycol grafted modified cellulose nanocrystals, the modified cellulose nanocrystals are introduced into polyurethane, so that the crystallization activation energy of polyurethane is reduced, the crystallization temperature of polyurethane is reduced, the crystallization nucleation of polyurethane is promoted, and polyethylene glycol is grafted to the cellulose nanocrystals, so that the compatibility of the cellulose nanocrystals and polyurethane can be effectively improved, and the interaction between molecular chains is enhanced, thereby enhancing the strength of the cellulose nanocrystals.
The casein solution is blended with the modified cellulose nanocrystals and polyurethane, so that the casein solution reacts with hydrophilic groups such as amino groups, carboxyl groups and hydroxyl groups in the modified cellulose nanocrystals and the polyurethane, the water resistance and wet rubbing resistance of the paint are improved, and the polyurethane can block polar groups among casein molecular chains to form hydrogen bonds, so that the comprehensive properties such as extensibility and bending resistance of the film forming agent are improved, interaction between the casein and the modified cellulose nanocrystals is improved, the tensile property of the paint is improved, the elongation at break is increased, the corrosion resistance is improved, the bonding property is good, and the toughness is strong.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. The water-based nano waterproof coating is characterized by comprising the following material components in parts by weight:
90 parts of polyurethane;
5 parts of modified cellulose nanocrystalline;
3 parts of nano titanium dioxide;
25 parts of casein solution;
3 parts of graphene;
1.5 parts of film forming additive.
2. The water-based nano waterproof coating according to claim 1, wherein the modified cellulose nanocrystals are cellulose nanocrystals modified by polyethylene glycol grafting.
3. The water-based nano waterproof coating according to claim 2, wherein the mass ratio of the polyethylene glycol to the cellulose nanocrystals is 1-2:10.
4. the water-based nano waterproof coating according to claim 1, wherein the nano titanium dioxide surface is coated with aluminum hydroxide.
5. The water-based nano waterproof coating according to claim 1, wherein the film-forming auxiliary agent comprises a composition of diatomite, silica gel and triethylene glycol monomethyl ether, and the mass ratio of the diatomite to the silica gel to the triethylene glycol monomethyl ether is 49:100:1.
6. the water-based nano waterproof coating according to claim 1, wherein the casein solution comprises an aqueous solution of casein, and the mass fraction of casein to water is 1:9-10.
7. The method for preparing the water-based nano waterproof paint according to any one of claims 1 to 6, comprising the following steps:
step 1, preparing modified cellulose nanocrystals;
step 2, blending polyurethane, casein solution and modified cellulose nanocrystalline in a solvent to obtain a component A;
step 3, mixing nano titanium dioxide, graphene and a film forming auxiliary agent in a solvent to obtain a component B;
and step 4, mixing the component A and the component B, and regulating the viscosity to obtain the water-based nano waterproof coating.
8. The method for preparing the water-based nano waterproof coating according to claim 7, wherein the method for preparing the modified cellulose nanocrystals comprises the following steps:
step 1, dissolving cellulose nanocrystalline powder in water to form a dissolving solution;
step 2, dropwise adding an alkaline solution into the dissolution solution, and stirring for 20-40min;
and step 3, adding the small molecular weight polyethylene glycol into the dissolution liquid, heating at 60-70 ℃, and stirring for 6-8h to obtain the modified cellulose nanocrystalline.
9. The method for preparing the water-based nano waterproof paint according to claim 7, wherein the viscosity is adjusted by using a mixed solvent comprising acetone and ethyl acetate in a mass ratio of 1:1.
10. Use of an aqueous nano waterproof coating according to any one of claims 1-6 in walls and metal surfaces.
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