A wear-resistant waterproof coating, preparation method and application in construction

Abstract

The present invention relates to the technical field of coatings, and discloses a wear-resistant waterproof coating, a preparation method and an application in construction. The preparation method includes: mixing polypropylene glycol, functionalized nano-silica, isophorone diisocyanate, and 4,4'-dihydroxydiphenyl disulfide to obtain a polyurethane prepolymer; mixing isophorone diisocyanate, amino-terminated polyether amine, and modified pyrene derivatives to obtain a polyurea prepolymer; mixing 2,4,6-triaminopyrimidine and silicone-modified epoxy resin to obtain a chain extender; mixing polyurethane prepolymer, polyurea prepolymer, chain extender, and hydroxyethyl methacrylate, adding a photoinitiator, and obtaining a wear-resistant waterproof coating. The coating has wear resistance and waterproofness, good comprehensive performance, and can be applied to architectural coatings.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a wear-resistant and waterproof coating, a preparation method and application in construction. Background Art

[0002] Paint is a substance that can be applied to the surface of an object using a specific construction method and can form a continuous coating film after curing. It can also protect and decorate the coated object through the coating film. Polymer waterproof coatings are solvent-based, water-based or powder-based waterproof coatings made of polymers as the main film-forming substances and various additives. They occupy an important position in the current waterproofing field and are an indispensable part of building waterproofing. When waterproof coatings are applied to the base of a building, they can form a continuous, overall tough and thick waterproof layer after curing, which improves the waterproofing effect.

[0003] At present, the coating industry not only needs coatings with good waterproof effects, but also requires coatings with properties such as wear resistance to meet the development needs of the coating industry. Polyurethane waterproof coatings have excellent performance, good wear resistance and comprehensive performance, good flexibility and substrate adhesion, and have been widely used in the construction industry. Inorganic materials have the characteristics of high hardness, high wear resistance and stable thermochemical properties. Effectively combining inorganic materials with polyurethane waterproof coatings to form composite coatings can achieve complementary advantages and meet the development needs of the coating industry.

[0004] Prior art, such as Chinese patent application CN101220241A, discloses a two-component high-strength polyurethane waterproof coating, which uses polyether polyol and diphenylmethane diisocyanate as base resins, and adds various additives and auxiliaries to make the prepared polyurethane waterproof coating have better comprehensive performance. However, in the obtained polyurethane coating, the reinforcing agent component is white carbon black, which is an inorganic particle with low compatibility with the base resin and is easy to agglomerate, affecting the comprehensive performance of the coating and limiting its application. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a wear-resistant waterproof coating, a preparation method and application in construction. The coating has wear resistance and waterproofness, good comprehensive performance, and can be applied to architectural coatings.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a wear-resistant waterproof coating comprises the following steps:

[0008] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0009] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0010] S11, mixing nano-silica with water, ultrasonically dispersing, adding ethanol and γ-aminopropyltriethoxysilane, reacting, centrifuging, filtering, washing, and drying to obtain amino nano-silica;

[0011] Mixing amino nano-silica, vanillin and water, adding an alkaline regulator to adjust the pH value, reacting, adding an acidic regulator to adjust the pH value to neutral after the reaction, filtering, washing and drying to obtain functionalized nano-silica;

[0012] S12, mixing polypropylene glycol and functionalized nano-silica, adding isophorone diisocyanate and dibutyltin dilaurate, reacting, after the reaction is completed, adding 4,4'-dihydroxydiphenyl disulfide, continuing the reaction, after the reaction is completed, obtaining a polyurethane prepolymer;

[0013] The preparation of polyurea prepolymer comprises the following steps:

[0014] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide and tetramethylammonium bromide are mixed and reacted. After the reaction is completed, a reaction product is obtained, purified and dried to obtain a pyrene derivative; the pyrene derivative, 2-mercaptoethanol, tetrahydrofuran and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed and reacted. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation to obtain a modified pyrene derivative;

[0015] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting, adding a modified pyrene derivative after the reaction, continuing the reaction, and obtaining a polyurea prepolymer after the reaction;

[0016] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether and lithium bromide, react, and after the reaction is completed, pass through a column to obtain modified silane;

[0017] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole are mixed and reacted, and after the reaction is completed, an organosilicon-modified epoxy resin is obtained; 2,4,6-triaminopyrimidine, organosilicon-modified epoxy resin and acetone are mixed and reacted, and after the reaction is completed, the solvent acetone is removed by rotary evaporation to obtain a chain extender;

[0018] Step three: mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react, add hydroxyethyl methacrylate after the reaction, continue the reaction, cool to room temperature after the reaction, add photoinitiator and stir to obtain a wear-resistant and waterproof coating.

[0019] Preferably, when preparing the polyurethane prepolymer, in S11: the mass ratio of nano-silica, water, ethanol, and γ-aminopropyltriethoxysilane is 10:300-350:10-12:3-4; when preparing amino nano-silica, the reaction conditions are: reacting at a temperature of 40-50° C. for 10-14 hours.

[0020] Preferably, when preparing the polyurethane prepolymer, in S11: the mass ratio of amino nano-silica, vanillin and water is 10:8-10:280-300; when preparing functionalized nano-silica, the reaction conditions are: reacting at a pH value of 10-11 and room temperature for 24-26 hours.

[0021] Preferably, the alkaline regulator includes 1 mol / L sodium hydroxide aqueous solution, and the acidic regulator includes 1 mol / L hydrogen chloride aqueous solution; when preparing functionalized nano-silica, the washing liquid used in the washing operation includes chloroform.

[0022] Preferably, when preparing the polyurethane prepolymer, in S12: the mass ratio of polypropylene glycol to functionalized nano-silica is 15:1; the molar ratio of polypropylene glycol, isophorone diisocyanate, and 4,4'-dihydroxydiphenyl disulfide is 1.5:4-4.5:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol; the reaction conditions are: reacting at a temperature of 70-80°C for 3-4h in a nitrogen atmosphere; and the continued reaction conditions are: continuing the reaction at a temperature of 60-70°C for 2-3h in a nitrogen atmosphere.

[0023] Preferably, when preparing the polyurea prepolymer, in S21: the mass ratio of 1-hydroxypyrene, epichlorohydrin, sodium hydroxide and tetramethylammonium bromide is 20-22:45-50:8-8.2:0.1-0.15; when preparing the pyrene derivative, the reaction conditions are: reacting at a temperature of 60-65°C for 4-5h.

[0024] Preferably, the purification operation comprises: adding water to the reaction product to wash it to neutrality, separating the liquids, taking the organic phase, and removing the solvent epichlorohydrin by rotary evaporation at a temperature of 80-90°C.

[0025] Preferably, when preparing the polyurea prepolymer, in S21: the mass ratio of pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene is 10-11:3.2-3.3:40-50:0.2-0.3; when preparing the modified pyrene derivative, the reaction conditions are: react at a temperature of 55-65°C for 4-5h.

[0026] Preferably, when preparing the polyurea prepolymer, in S22: the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 90-100:180-200:8-10; the reaction conditions are: reacting for 2-3 hours in a nitrogen atmosphere at a temperature of 55-65°C; and the continued reaction conditions are: continuing the reaction for 3-4 hours in a nitrogen atmosphere at a temperature of 65-70°C.

[0027] Preferably, in step 2: the mass ratio of cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide is 9-10:1.8-2:0.5-0.6; when preparing the modified silane, the reaction conditions are: stirring the reaction at room temperature in a nitrogen atmosphere for 48-52 hours.

[0028] Preferably, the developing solvent used in the column operation is a mixture of ethyl acetate, petroleum ether, dichloromethane and methanol in a volume ratio of 6:2:10:1.

[0029] Preferably, in the step 2: the mass ratio of modified silane, epoxy resin, triethylamine, and p-hydroxyanisole is 4-5:35-40:0.1-0.2:0.02-0.03; when preparing the silicone-modified epoxy resin, the reaction conditions are: reacting at 90-95°C for 3-4h; the mass ratio of 2,4,6-triaminopyrimidine, silicone-modified epoxy resin, and acetone is 10:15-20:40-50; when preparing the chain extender, the reaction conditions are: reacting at 30-40°C for 8-10h.

[0030] Preferably, in the step three: the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate, and photoinitiator is 90-100:50-60:8-10:0.03-0.05:60-70:14-16:6-8; the reaction conditions are: reacting for 1-2 hours in a nitrogen atmosphere at a temperature of 65-70°C; and the continued reaction conditions are: continuing the reaction for 0.5-1 hour in a nitrogen atmosphere at a temperature of 65-70°C.

[0031] Preferably, a wear-resistant waterproof coating is prepared using the method for preparing the wear-resistant waterproof coating as described above.

[0032] Preferably, an application of the wear-resistant and waterproof coating as described above in buildings.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] The invention uses a condensation reaction of an aminosilane coupling agent with vanillin to generate a Schiff base bond, grafts vanillin on the surface of the amino nano-silica, and obtains a functionalized nano-silica with a Schiff base bond and a phenolic hydroxyl group. The active groups on the surface of the functionalized nano-silica react and copolymerize with isocyanate groups, so that the functionalized nano-silica is used as a copolymer monomer to participate in the preparation of a polyurethane prepolymer, copolymerizes inorganic rigid particles on the main chain of the polyurethane prepolymer, and improves the dispersibility of the functionalized nano-silica and the wear resistance of the matrix.

[0035] Among them, the Schiff base bond of functionalized nano-silica has antibacterial activity and can improve the antibacterial properties of the matrix. At the same time, the Schiff base bond is a dynamic reversible bond with self-repairing ability, which can synergistically improve the mechanical properties of the matrix resin with the dynamic disulfide bond of 4,4'-dihydroxydiphenyl disulfide.

[0036] The present invention reacts 1-hydroxypyrene with epichlorohydrin to obtain a pyrene derivative having an epoxy group, and the epoxy group is reacted with the mercapto group of 2-mercaptoethanol to open the epoxy group to obtain a modified pyrene derivative having a dihydroxy group, and the dihydroxy group of the modified pyrene derivative is polymerized with an isocyanate group to obtain a polyurea prepolymer. The pyrene group has a rigid structure and a π-π conjugated effect of an aromatic compound and has excellent optical transmittance in the visible light region, so the wear resistance and comprehensive performance of the polyurea prepolymer are improved.

[0037] The invention adopts the reaction of the secondary amine of cyclohexylaminopropyltrimethoxysilane with the epoxy group of ethylene glycol diglycidyl ether, and the epoxy group is ring-opened to obtain a modified silane having double terminal hydroxyl groups and side chain siloxane segments; the hydroxyl groups of the modified silane and the epoxy group of the epoxy resin are further subjected to ring-opening reaction to introduce the siloxane segments into the epoxy resin to obtain an organosilicon-modified epoxy resin; the amino groups of 2,4,6-triaminopyrimidine and the epoxy group of the organosilicon-modified epoxy resin are reacted to obtain a chain extender having a siloxane segment, an epoxy resin structure and multiple amino groups; wherein the siloxane The alkane chain segment can improve the water resistance and adhesion of the matrix resin; the epoxy resin has excellent mechanical properties and weather resistance, which can improve the wear resistance and comprehensive performance of the matrix resin; the three primary amino groups in 2,4,6-triaminopyrimidine generate secondary amines after the ring-opening reaction, and both the secondary amines and the primary amino groups can further react with the isocyanate-terminated prepolymer to increase the crosslinking degree of the matrix resin as a chain extender and improve the mechanical properties. At the same time, the pyrimidine structure has certain antibacterial properties, which can improve the antibacterial properties of the matrix resin together with the Schiff base bond of the functionalized nano-silica.

[0038] The invention introduces double bond groups after mixing polyurethane prepolymer, polyurea prepolymer and chain extender, and then mixing and reacting with hydroxyethyl methacrylate. The double bonds serve as ultraviolet curing groups to endow the matrix resin with photocuring ability. Photocuring can be achieved by adding a photoinitiator. The obtained coating has wear resistance and water resistance, good comprehensive performance, and can be applied to architectural coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a process flow chart for preparing the wear-resistant and waterproof coating in the present invention;

[0040] Figure 2 It is a line graph of water absorption rate of the coatings prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention in performance tests;

[0041] Figure 3 It is a line graph of the impact strength of the coatings prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention in performance tests. DETAILED DESCRIPTION

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0043] Example 1

[0044] This embodiment discloses a method for preparing a wear-resistant and waterproof coating, comprising the following steps:

[0045] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0046] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0047] S11, mixing nano-silica with water, ultrasonically dispersing for 1 hour, adding ethanol and γ-aminopropyltriethoxysilane, the mass ratio of nano-silica, water, ethanol, and γ-aminopropyltriethoxysilane is 10:320:11:3.5, reacting at 45°C for 12 hours, centrifuging and filtering after the reaction, taking the filter cake, adding ethanol 6 times the mass of the filter cake to wash three times, and drying at 55°C for 22 hours to obtain amino nano-silica;

[0048] Amino nano-silica, vanillin and water were mixed in a mass ratio of 10:8:280, and a 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10, and the mixture was reacted at room temperature for 24 hours. After the reaction, a 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and chloroform in an amount of 5 times the mass of the filter cake was added to wash the filter cake, and the mixture was dried at 50°C for 24 hours to obtain functionalized nano-silica.

[0049] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 4 hours. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 60° C. for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained;

[0050] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0051] The preparation of polyurea prepolymer comprises the following steps:

[0052] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide are mixed in a mass ratio of 20:45:8:0.1, and reacted at 60°C for 5 hours. After the reaction is completed, water is added to wash until neutral, and the liquids are separated. The organic phase is taken, and the solvent epichlorohydrin is removed by rotary evaporation at 80°C, and dried at 90°C for 10 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed in a mass ratio of 10:3.2:40:0.2, and reacted at 55°C for 5 hours. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 40°C to obtain a modified pyrene derivative;

[0053] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 55°C for 3 hours, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 65°C for 4 hours, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 90:180:8;

[0054] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 9:1.8:0.5, stir and react for 48 hours in a nitrogen atmosphere at room temperature, and after the reaction is completed, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0055] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 4:35:0.1:0.02, and reacted at 90° C. for 4 hours. After the reaction was completed, an organosilicon-modified epoxy resin was obtained;

[0056] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:15:40, and reacted at 30°C for 10 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 35°C to obtain a chain extender;

[0057] Step 3: Mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react for 2 hours in a nitrogen atmosphere at 65°C, add hydroxyethyl methacrylate after the reaction, continue to react for 1 hour in a nitrogen atmosphere at 65°C, cool to room temperature after the reaction, add a photoinitiator and stir for 20 minutes in a light-proof environment to obtain a wear-resistant and waterproof coating;

[0058] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 90:60:8:0.03:60:14:6.

[0059] Example 2

[0060] This embodiment discloses a method for preparing a wear-resistant and waterproof coating, comprising the following steps:

[0061] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0062] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0063] S11, amino nano-silica, vanillin, and water were mixed in a mass ratio of 10:8.5:285, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10, and the mixture was reacted at room temperature for 24 hours. After the reaction, 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and chloroform in an amount of 5 times the mass of the filter cake was added to wash the filter cake, and the mixture was dried at 55° C. for 22 hours to obtain functionalized nano-silica; wherein the preparation of amino nano-silica was the same as that in Example 1;

[0064] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 75°C for 3.5 hours. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 65°C for 2.5 hours. After the reaction is completed, a polyurethane prepolymer is obtained;

[0065] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4.2:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0066] The preparation of polyurea prepolymer comprises the following steps:

[0067] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide are mixed in a mass ratio of 20.5:46:8:0.1, and reacted at 60°C for 4.5 hours. After the reaction is completed, water is added to wash until neutral, and the liquids are separated. The organic phase is taken, and the solvent epichlorohydrin is removed by rotary evaporation at 85°C, and dried at 95°C for 10 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed in a mass ratio of 10.2:3.2:40:0.2, and reacted at 60°C for 4.5 hours. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 45°C to obtain a modified pyrene derivative;

[0068] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 58°C for 3 hours, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 68°C for 3.5 hours, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 93:185:8.5;

[0069] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 9.2:1.85:0.5, stir and react for 50 hours in a nitrogen atmosphere at room temperature, and after the reaction is completed, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0070] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 4.2:36:0.1:0.02, and reacted at 90° C. for 4 hours. After the reaction was completed, a silicone-modified epoxy resin was obtained;

[0071] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:16:42, and reacted at 35°C for 9 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 40°C to obtain a chain extender;

[0072] Step 3: Mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react for 1.5 hours in a nitrogen atmosphere at 65°C, add hydroxyethyl methacrylate after the reaction, continue to react for 0.8 hours in a nitrogen atmosphere at 68°C, cool to room temperature after the reaction, add a photoinitiator and stir for 20 minutes in a light-proof environment to obtain a wear-resistant and waterproof coating;

[0073] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 92:58:8.5:0.03:62:14.5:6.

[0074] Example 3

[0075] This embodiment discloses a method for preparing a wear-resistant and waterproof coating, comprising the following steps:

[0076] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0077] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0078] S11, amino nano-silica, vanillin, and water were mixed in a mass ratio of 10:9:290, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10.5, and the mixture was reacted at room temperature for 25 hours. After the reaction, 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and chloroform in an amount of 6 times the mass of the filter cake was added to wash the filter cake, and the mixture was dried at 55° C. for 22 hours to obtain functionalized nano-silica; wherein the preparation of amino nano-silica was the same as that in Example 1;

[0079] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 75°C for 3.5 hours. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 65°C for 2.5 hours. After the reaction is completed, a polyurethane prepolymer is obtained;

[0080] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4.3:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0081] The preparation of polyurea prepolymer comprises the following steps:

[0082] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide are mixed in a mass ratio of 21:48:8.1:0.13, and reacted at 63°C for 4.5 hours. After the reaction is completed, water is added to wash until neutral, and the liquids are separated. The organic phase is taken, and the solvent epichlorohydrin is removed by rotary evaporation at 85°C, and dried at 95°C for 9 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed in a mass ratio of 10.5:3.2:45:0.25, and reacted at 60°C for 4.5 hours. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 45°C to obtain a modified pyrene derivative;

[0083] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 60°C for 2.5 hours, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 68°C for 3.5 hours, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 95:190:9;

[0084] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 9.5:1.9:0.55, stir and react for 50 hours in a nitrogen atmosphere at room temperature, and after the reaction is completed, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0085] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 4.5:38:0.15:0.02, and reacted at 92° C. for 3.5 hours. After the reaction was completed, a silicone-modified epoxy resin was obtained;

[0086] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:18:45, and reacted at 35°C for 9 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 40°C to obtain a chain extender;

[0087] Step 3: Mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react for 1.5 hours in a nitrogen atmosphere at 68°C, add hydroxyethyl methacrylate after the reaction, continue to react for 0.8 hours in a nitrogen atmosphere at 68°C, cool to room temperature after the reaction, add a photoinitiator in a light-proof environment and stir for 25 minutes to obtain a wear-resistant and waterproof coating;

[0088] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 95:55:9:0.04:65:15:7.

[0089] Example 4

[0090] This embodiment discloses a method for preparing a wear-resistant and waterproof coating, comprising the following steps:

[0091] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0092] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0093] S11, amino nano-silica, vanillin, and water were mixed in a mass ratio of 10:9.5:295, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 11, and the mixture was reacted at room temperature for 26 hours. After the reaction, 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and 8 times the mass of the filter cake was added to wash the filter cake with chloroform, and the mixture was dried at 55° C. for 22 hours to obtain functionalized nano-silica; wherein the preparation of amino nano-silica was the same as that in Example 1;

[0094] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 75°C for 3.5 hours. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 65°C for 2.5 hours. After the reaction is completed, a polyurethane prepolymer is obtained;

[0095] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4.4:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0096] The preparation of polyurea prepolymer comprises the following steps:

[0097] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide are mixed in a mass ratio of 21.5:49:8.2:0.15, and reacted at 65°C for 4.5 hours. After the reaction is completed, water is added to wash until neutral, and the liquids are separated. The organic phase is taken, and the solvent epichlorohydrin is removed by rotary evaporation at 85°C, and dried at 95°C for 9 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed in a mass ratio of 10.8:3.25:48:0.28, and reacted at 60°C for 4.5 hours. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 45°C to obtain a modified pyrene derivative;

[0098] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 65°C for 2.5 hours, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 70°C for 3.5 hours, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 98:195:9.5;

[0099] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 9.8:1.95:0.55, stir and react for 50 hours in a nitrogen atmosphere at room temperature, and after the reaction, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0100] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 4.8:39:0.2:0.03, and reacted at 95° C. for 3.5 hours. After the reaction was completed, a silicone-modified epoxy resin was obtained;

[0101] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:19:48, and reacted at 35°C for 9 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 40°C to obtain a chain extender;

[0102] Step 3: Mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react for 1.5 hours in a nitrogen atmosphere at 70°C, add hydroxyethyl methacrylate after the reaction, continue to react for 0.8 hours in a nitrogen atmosphere at 70°C, cool to room temperature after the reaction, add a photoinitiator and stir for 25 minutes in a light-proof environment to obtain a wear-resistant and waterproof coating;

[0103] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 98:52:9.5:0.04:68:15.5:7.

[0104] Example 5

[0105] This embodiment discloses a method for preparing a wear-resistant and waterproof coating, comprising the following steps:

[0106] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0107] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0108] S11, amino nano-silica, vanillin, and water were mixed in a mass ratio of 10:10:300, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 11, and the mixture was reacted at room temperature for 26 hours. After the reaction, 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and 8 times the mass of the filter cake was added to wash the filter cake with chloroform, and the mixture was dried at 60° C. for 20 hours to obtain functionalized nano-silica; wherein the preparation of amino nano-silica was the same as that in Example 1;

[0109] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 80° C. for 3 h. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 2 h. After the reaction is completed, a polyurethane prepolymer is obtained;

[0110] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4.5:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0111] The preparation of polyurea prepolymer comprises the following steps:

[0112] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide are mixed in a mass ratio of 22:50:8.2:0.15, and reacted at 65°C for 4 hours. After the reaction is completed, water is added to wash until neutral, and the liquid is separated. The organic phase is taken, and the solvent epichlorohydrin is removed by rotary evaporation at 90°C, and dried at 100°C for 8 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed in a mass ratio of 11:3.3:50:0.3, and reacted at 65°C for 4 hours. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 50°C to obtain a modified pyrene derivative;

[0113] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 65°C for 2h, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 70°C for 3h, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine and modified pyrene derivative is 100:200:10;

[0114] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 10:2:0.6, stir and react for 52 hours in a nitrogen atmosphere at room temperature, and after the reaction is completed, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0115] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 5:40:0.2:0.03, and reacted at 95° C. for 3 hours. After the reaction was completed, an organosilicon-modified epoxy resin was obtained;

[0116] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:20:50, and reacted at 40°C for 8 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 45°C to obtain a chain extender;

[0117] Step 3: Mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react for 1 h in a nitrogen atmosphere at 70°C, add hydroxyethyl methacrylate after the reaction, continue to react for 0.5 h in a nitrogen atmosphere at 70°C, cool to room temperature after the reaction, add a photoinitiator in a light-proof environment and stir for 30 min to obtain a wear-resistant and waterproof coating;

[0118] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 100:50:10:0.05:70:16:8.

[0119] Comparative Example 1

[0120] This comparative example discloses a method for preparing a coating, comprising the following steps:

[0121] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0122] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0123] Polypropylene glycol, isophorone diisocyanate and dibutyltin dilaurate were mixed, reacted in a nitrogen atmosphere at 70°C for 4 hours, and after the reaction, 4,4'-dihydroxydiphenyl disulfide was added, and the reaction was continued in a nitrogen atmosphere at 60°C for 3 hours. After the reaction, a polyurethane prepolymer was obtained;

[0124] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0125] The preparation of polyurea prepolymer comprises the following steps:

[0126] S11, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide were mixed in a mass ratio of 20:45:8:0.1, and reacted at 60°C for 5 hours. After the reaction was completed, water was added to wash until neutral, and the liquids were separated. The organic phase was taken, and the solvent epichlorohydrin was removed by rotary evaporation at 80°C, and dried at 90°C for 10 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene were mixed in a mass ratio of 10:3.2:40:0.2, and reacted at 55°C for 5 hours. After the reaction was completed, the solvent tetrahydrofuran was removed by rotary evaporation at 40°C to obtain a modified pyrene derivative;

[0127] S12, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 55°C for 3 hours, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 65°C for 4 hours, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 90:180:8;

[0128] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 9:1.8:0.5, stir and react for 48 hours in a nitrogen atmosphere at room temperature, and after the reaction is completed, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0129] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 4:35:0.1:0.02, and reacted at 90° C. for 4 hours. After the reaction was completed, an organosilicon-modified epoxy resin was obtained;

[0130] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:15:40, and reacted at 30°C for 10 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 35°C to obtain a chain extender;

[0131] Step 3: Mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react for 2 hours in a nitrogen atmosphere at 65°C, add hydroxyethyl methacrylate after the reaction, continue to react for 1 hour in a nitrogen atmosphere at 65°C, cool to room temperature after the reaction, add a photoinitiator in a light-proof environment and stir for 20 minutes to obtain a coating;

[0132] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 90:60:8:0.03:60:14:6.

[0133] Comparative Example 2

[0134] This comparative example discloses a method for preparing a coating, comprising the following steps:

[0135] Step 1, preparing polyurethane prepolymer and polyurea prepolymer;

[0136] Wherein, the preparation of polyurethane prepolymer comprises the following steps:

[0137] S11, amino nano-silica, vanillin, and water were mixed in a mass ratio of 10:8:280, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10, and the mixture was reacted at room temperature for 24 hours. After the reaction was completed, 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and chloroform in an amount of 5 times the mass of the filter cake was added to wash the filter cake, and the mixture was dried at 50° C. for 24 hours to obtain functionalized nano-silica; wherein the preparation of amino nano-silica was the same as that in Example 1;

[0138] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 4 hours. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 60° C. for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained;

[0139] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0140] The preparation of polyurea prepolymer comprises the following steps:

[0141] S21, 1-hydroxypyrene, epichlorohydrin, sodium hydroxide, and tetramethylammonium bromide are mixed in a mass ratio of 20:45:8:0.1, and reacted at 60°C for 5 hours. After the reaction is completed, water is added to wash until neutral, and the liquids are separated. The organic phase is taken, and the solvent epichlorohydrin is removed by rotary evaporation at 80°C, and dried at 90°C for 10 hours to obtain a pyrene derivative; a pyrene derivative, 2-mercaptoethanol, tetrahydrofuran, and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed in a mass ratio of 10:3.2:40:0.2, and reacted at 55°C for 5 hours. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at 40°C to obtain a modified pyrene derivative;

[0142] S22, mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting in a nitrogen atmosphere at 55°C for 3 hours, adding a modified pyrene derivative after the reaction, and continuing to react in a nitrogen atmosphere at 65°C for 4 hours, and obtaining a polyurea prepolymer after the reaction; wherein the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 90:180:8;

[0143] Step 2: Mix the polyurethane prepolymer, polyurea prepolymer, dibutyltin dilaurate and acetone, add hydroxyethyl methacrylate, react for 1 hour at 65° C. in a nitrogen atmosphere, cool to room temperature after the reaction, add a photoinitiator and stir for 20 minutes in a light-proof environment to obtain a coating;

[0144] Among them, the mass ratio of polyurethane prepolymer, polyurea prepolymer, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 90:60:0.03:60:14:6.

[0145] Comparative Example 3

[0146] This comparative example discloses a method for preparing a coating, comprising the following steps:

[0147] Step 1, preparing a polyurethane prepolymer;

[0148] S11, amino nano-silica, vanillin, and water were mixed in a mass ratio of 10:8:280, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10, and the mixture was reacted at room temperature for 24 hours. After the reaction was completed, 1 mol / L hydrogen chloride aqueous solution was added to adjust the pH value to neutral, and the mixture was filtered to obtain a filter cake, and chloroform in an amount of 5 times the mass of the filter cake was added to wash the filter cake, and the mixture was dried at 50° C. for 24 hours to obtain functionalized nano-silica; wherein the preparation of amino nano-silica was the same as that in Example 1;

[0149] S12, polypropylene glycol and functionalized nano-silica are mixed in a mass ratio of 15:1, isophorone diisocyanate and dibutyltin dilaurate are added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 4 hours. After the reaction is completed, 4,4'-dihydroxydiphenyl disulfide is added, and the mixture is reacted in a nitrogen atmosphere at a temperature of 60° C. for 3 hours. After the reaction is completed, a polyurethane prepolymer is obtained;

[0150] The molar ratio of polypropylene glycol, isophorone diisocyanate and 4,4'-dihydroxydiphenyl disulfide is 1.5:4:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol;

[0151] Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide in a mass ratio of 9:1.8:0.5, stir and react for 48 hours in a nitrogen atmosphere at room temperature, and after the reaction is completed, pass through a column to obtain modified silane; wherein the developing solvent used in the column operation is ethyl acetate, petroleum ether, dichloromethane, and methanol mixed in a volume ratio of 6:2:10:1;

[0152] The modified silane, epoxy resin, triethylamine and p-hydroxyanisole were mixed in a mass ratio of 4:35:0.1:0.02, and reacted at 90° C. for 4 hours. After the reaction was completed, an organosilicon-modified epoxy resin was obtained;

[0153] 2,4,6-triaminopyrimidine, silicone-modified epoxy resin and acetone were mixed in a mass ratio of 10:15:40, and reacted at 30°C for 10 hours. After the reaction, the solvent acetone was removed by rotary evaporation at 35°C to obtain a chain extender;

[0154] Step 3: Mix the polyurethane prepolymer, chain extender, dibutyltin dilaurate and acetone, and react them in a nitrogen atmosphere at 65°C for 2 hours. After the reaction, add hydroxyethyl methacrylate, and continue to react in a nitrogen atmosphere at 65°C for 1 hour. After the reaction, cool to room temperature, add a photoinitiator and stir for 20 minutes in a light-proof environment to obtain a coating;

[0155] Among them, the mass ratio of polyurethane prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 150:8:0.03:60:14:6.

[0156] In the above embodiments and comparative examples: nano-silicon dioxide comes from Hangzhou Hengge Nano Technology Co., Ltd., with an average particle size of 30 nm; vanillin comes from Alfa Aesar, CAS No.: 121-33-5; polypropylene glycol comes from Shanghai Aladdin Biochemical Technology Co., Ltd., with item No. P103208; 4,4'-dihydroxydiphenyl disulfide comes from Nanjing Chemical Reagent Co., Ltd., with item No. C0656559467, CAS No.: 15015-57-3; 1-hydroxypyrene comes from Shanghai Aladdin Biochemical Technology Co., Ltd., with item No. H119988, CAS No.: 5315-79-7; amino-terminated polyetheramine comes from Mitsui Chemicals Co., Ltd., model Amino-terminated polyetheramine D-2000; cyclohexylaminopropyltrimethoxysilane is from Shanghai MacLean Biochemical Technology Co., Ltd., product number N924015, CAS number: 3068-78-8; epoxy resin is from Baling Petrochemical Company, model bisphenol A epoxy resin E-44; 2,4,6-triaminopyrimidine is from Shandong Guohua Chemical Co., Ltd., CAS number: 1004-38-2; photoinitiator is from Jiangsu Runfeng Synthetic Technology Co., Ltd., model photoinitiator 1173, CAS number: 7374-98-5.

[0157] Test example

[0158] The coatings prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to comprehensive performance tests. The specific test results are shown in Table 1:

[0159] Table 1

[0160]

[0161]

[0162] The tests of various indicators in Table 1 are based on the following standards: water absorption is determined by referring to HGT3344-1985 "Determination of water absorption of paint films"; adhesion is determined by referring to GB / T1720-1989 "Determination of adhesion of paint films"; impact strength is determined by referring to GB / T1732-2020 "Determination of impact resistance of paint films"; RCA abrasion is determined by Norman RCA abrasion tester with a load of 175g; antibacterial rate is determined by referring to GB / T21866-2008 "Determination of antibacterial properties and antibacterial effects of antibacterial coatings (paint films)".

[0163] It can be seen from the test results in Table 1 that the wear-resistant and waterproof coating prepared by the present invention has wear resistance and waterproofness, and has good comprehensive performance.

[0164] Nano-silica modified by aminosilane coupling agent and vanillin generate Schiff base bonds through condensation reaction of amino group and aldehyde group, and obtain functionalized nano-silica with Schiff base bonds and phenolic hydroxyl group, which is copolymerized with isocyanate group to improve the dispersibility of functionalized nano-silica and the wear resistance of matrix. Among them, the Schiff base bond of functionalized nano-silica not only has antibacterial activity, but also can improve the antibacterial property of matrix. At the same time, the Schiff base bond is a dynamic reversible bond with self-repairing ability, which can cooperate with the dynamic disulfide bond of 4,4'-dihydroxydiphenyl disulfide to improve the mechanical properties of matrix resin. In comparative example 1, no functionalized silica is added, and the improvement effect of inorganic rigid particles on wear resistance is lacking. Moreover, the Schiff base bond in functionalized nano-silica not only has antibacterial activity, but also can cooperate with the dynamic disulfide bond of 4,4'-dihydroxydiphenyl disulfide to improve the mechanical properties of matrix resin, so the wear resistance, antibacterial property and mechanical properties of comparative example 1 are lower than those of the embodiment.

[0165] The chain extender has siloxane segments, epoxy resin structures and multiple amino groups. The siloxane segments can improve the water resistance and adhesion of the matrix resin; the epoxy resin has excellent mechanical properties and weather resistance and wear resistance, which can improve the wear resistance and comprehensive performance of the matrix resin; the three primary amino groups in 2,4,6-triaminopyrimidine generate secondary amines after the ring-opening reaction, and both the secondary amines and the primary amino groups can further react with the isocyanate-terminated prepolymer, as a chain extender to increase the crosslinking degree of the matrix resin and improve the mechanical properties. At the same time, the pyrimidine structure has certain antibacterial properties, which can improve the antibacterial properties of the matrix resin together with the Schiff base bond of the functionalized nano-silica. In Comparative Example 2, no chain extender is added, the crosslinking degree of the matrix resin is reduced, the mechanical properties are reduced, and the antibacterial properties of the pyrimidine structure in the chain extender and the siloxane segments and epoxy resin structures are lacking to improve the water resistance, wear resistance and adhesion, so the comprehensive performance of Comparative Example 2 is lower than that of the embodiment.

[0166] The modified pyrene derivative in the polyurea prepolymer has a pyrene group, which has a rigid structure and π-π conjugated effect of aromatic compounds. Adding it to the base resin can improve the wear resistance and mechanical properties of the coating. In Comparative Example 3, no polyurea prepolymer is added, and the polyurea prepolymer lacks the effect of improving the mechanical properties and wear resistance of the base resin. The wear resistance and mechanical properties of Comparative Example 3 are lower than those of the embodiment.

[0167] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a wear-resistant and waterproof coating, characterized in that: The following steps are involved: Step 1, preparing polyurethane prepolymer and polyurea prepolymer; Wherein, the preparation of polyurethane prepolymer comprises the following steps: S11, mixing amino nano-silica, vanillin and water, adding an alkaline regulator to adjust the pH value, reacting, and after the reaction is completed, adding an acidic regulator to adjust the pH value to neutral, filtering, washing, and drying to obtain functionalized nano-silica; S12, mixing polypropylene glycol and functionalized nano-silica, adding isophorone diisocyanate and dibutyltin dilaurate, reacting, after the reaction is completed, adding 4,4'-dihydroxydiphenyl disulfide, continuing the reaction, after the reaction is completed, obtaining a polyurethane prepolymer; The preparation of polyurea prepolymer comprises the following steps: 1-hydroxypyrene, epichlorohydrin, sodium hydroxide and tetramethylammonium bromide are mixed and reacted. After the reaction is completed, a reaction product is obtained, purified and dried to obtain a pyrene derivative; the pyrene derivative, 2-mercaptoethanol, tetrahydrofuran and 1,5,7-triazabicyclo (4.4.0) dec-5-ene are mixed and reacted. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation to obtain a modified pyrene derivative; Wherein, the mass ratio of 1-hydroxypyrene, epichlorohydrin, sodium hydroxide and tetramethylammonium bromide is 20-22:45-50:8-8.2:0.1-0.15; when preparing pyrene derivatives, the reaction conditions are: reacting at 60-65°C for 4-5h; the mass ratio of pyrene derivatives, 2-mercaptoethanol, tetrahydrofuran and 1,5,7-triazabicyclo (4.4.0) dec-5-ene is 10-11:3.2-3.3:40-50:0.2-0.3; when preparing modified pyrene derivatives, the reaction conditions are: reacting at 55-65°C for 4-5h; Mixing isophorone diisocyanate and amino-terminated polyetheramine, reacting, adding modified pyrene derivative after the reaction, continuing the reaction, and obtaining polyurea prepolymer after the reaction; Step 2: Mix cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether and lithium bromide, react, and after the reaction is completed, pass through a column to obtain modified silane; The modified silane, epoxy resin, triethylamine and p-hydroxyanisole are mixed and reacted, and after the reaction is completed, an organosilicon-modified epoxy resin is obtained; 2,4,6-triaminopyrimidine, organosilicon-modified epoxy resin and acetone are mixed and reacted, and after the reaction is completed, the solvent acetone is removed by rotary evaporation to obtain a chain extender; Step three: mix the polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate and acetone, react, add hydroxyethyl methacrylate after the reaction, continue the reaction, cool to room temperature after the reaction, add photoinitiator and stir to obtain a wear-resistant and waterproof coating.

2. The method for preparing a wear-resistant and waterproof coating according to claim 1, characterized in that: When preparing the polyurethane prepolymer, the amino nano-silica in S11 is prepared by the following steps: The nano-silicon dioxide is mixed with water, ultrasonically dispersed, ethanol and γ-aminopropyltriethoxysilane are added, reacted, centrifuged, filtered, washed and dried after the reaction is completed, and amino nano-silicon dioxide is obtained; The mass ratio of nano-silicon dioxide, water, ethanol and γ-aminopropyltriethoxysilane is 10:300-350:10-12:3-4; and the reaction conditions are: reacting at a temperature of 40-50° C. for 10-14 hours.

3. The method for preparing a wear-resistant and waterproof coating according to claim 1, characterized in that: When preparing the polyurethane prepolymer, in S11: the mass ratio of amino nano-silica, vanillin and water is 10:8-10:280-300; when preparing functionalized nano-silica, the reaction conditions are: reacting at a pH value of 10-11 and room temperature for 24-26 hours.

4. The method for preparing a wear-resistant and waterproof coating according to claim 1, characterized in that: When preparing the polyurethane prepolymer, in S12: the mass ratio of polypropylene glycol to functionalized nano-silica is 15:1; the molar ratio of polypropylene glycol, isophorone diisocyanate, and 4,4'-dihydroxydiphenyl disulfide is 1.5:4-4.5:0.5; the amount of dibutyltin dilaurate added is 0.05% of the mass of polypropylene glycol; the reaction conditions are: reacting for 3-4 hours in a nitrogen atmosphere at a temperature of 70-80°C; and the continued reaction conditions are: continuing the reaction for 2-3 hours in a nitrogen atmosphere at a temperature of 60-70°C.

5. The method for preparing a wear-resistant and waterproof coating according to claim 1, characterized in that: In the preparation of the polyurea prepolymer: the mass ratio of isophorone diisocyanate, amino-terminated polyetheramine, and modified pyrene derivative is 90-100:180-200:8-10; the reaction conditions are: reacting for 2-3 hours at a temperature of 55-65°C in a nitrogen atmosphere; and the continued reaction conditions are: continuing the reaction for 3-4 hours at a temperature of 65-70°C in a nitrogen atmosphere.

6. The method for preparing a wear-resistant and waterproof coating according to claim 1, characterized in that: In the step 2, the mass ratio of cyclohexylaminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, and lithium bromide is 9-10:1.8-2:0.5-0.6; when preparing modified silane, the reaction conditions are: stirring and reacting for 48-52 hours at room temperature in a nitrogen atmosphere; the mass ratio of modified silane, epoxy resin, triethylamine, and p-hydroxyanisole is 4-5:35-40:0.1-0.2:0.02-0.03; when preparing silicone-modified epoxy resin, the reaction conditions are: reacting at a temperature of 90-95°C for 3-4 hours; the mass ratio of 2,4,6-triaminopyrimidine, silicone-modified epoxy resin, and acetone is 10:15-20:40-50; when preparing a chain extender, the reaction conditions are: reacting at a temperature of 30-40°C for 8-10 hours.

7. The method for preparing a wear-resistant and waterproof coating according to claim 1, characterized in that: In the step three, the mass ratio of polyurethane prepolymer, polyurea prepolymer, chain extender, dibutyltin dilaurate, acetone, hydroxyethyl methacrylate and photoinitiator is 90-100:50-60:8-10:0.03-0.05:60-70:14-16:6-8; the reaction conditions are: reacting for 1-2 hours in a nitrogen atmosphere at a temperature of 65-70°C; and the continued reaction conditions are: continuing the reaction for 0.5-1 hour in a nitrogen atmosphere at a temperature of 65-70°C.

8. A wear-resistant waterproof coating prepared by the method for preparing a wear-resistant waterproof coating as described in any one of claims 1 to 7.

9. Use of the wear-resistant and waterproof coating as claimed in claim 8 in buildings.

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