High-temperature-resistant waterproof coating and preparation method thereof

Abstract

The application relates to the technical field of paint, and discloses a high-temperature-resistant waterproof paint and a preparation method thereof. The preparation method comprises the following steps: introducing hydroxyl-terminated nitrile rubber / montmorillonite composite material into water-based polyurethane acrylate by adding 4-(4-hydroxyphenyl) phthalazine-1-ol, N-(4-hydroxyphenyl) maleimide and perfluoro chain extender; and then, under the condition of an initiator, free radical polymerization is carried out on the obtained water-based polyurethane acrylate by adding monomer oxazolidinone acrylate containing a carbon-carbon double bond, gamma-methacryloyloxypropyltrimethoxysilane, methyl methacrylate hexafluorobutyl ester and styrene; the obtained paint has excellent high-temperature resistance and waterproof performance and good mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to a kind of high-temperature-resistant waterproof coating and preparation method thereof. BACKGROUND

[0002] Polyurethane waterproof coating is highly favored due to its excellent performance, and is one of the key development waterproof materials. Waterborne polyurethane is an environmentally friendly product using water as solvent. Compared with traditional solvent-based polyurethane coating, it has the advantages of safety, green and environmental protection. However, the water resistance of waterborne polyurethane is reduced due to the introduction of a large number of hydrophilic segments or hydrophilic groups. In addition, the traditional polyurethane-based coating has insufficient high-temperature resistance, and needs to be modified.

[0003] The prior art, such as Chinese patent CN101265318A, discloses a high-performance waterborne polyurethane dispersion and its application. By introducing a cyclic structure into the molecular chain of waterborne polyurethane, the comprehensive properties of water resistance and heat resistance of waterborne polyurethane are improved. However, the heat resistance of the prepared waterborne polyurethane can still be further improved. SUMMARY

[0004] The present application aims to overcome the shortcomings of the prior art and provide a high-temperature-resistant waterproof coating and a preparation method thereof. The coating has excellent heat resistance and waterproof performance, and good mechanical properties.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:

[0006] A preparation method of a high-temperature-resistant waterproof coating, comprising the following steps:

[0007] Step (1), diphenylmethane diisocyanate is mixed and dissolved with N,N-dimethylformamide, 4-(4-hydroxyphenyl) phthalazine-1-ol and stannous octoate are added, and the reaction is carried out. After the reaction is completed, the temperature is lowered, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material and 2,2-dimethylol propionic acid are added, and the reaction is continued. After the reaction is completed, perfluoro chain extender is added, and the reaction is carried out again. After the reaction is completed, N-(4-hydroxyphenyl) maleimide is added, and the end-capping reaction is carried out. After the reaction is completed, triethylamine is added for neutralization. After neutralization, the temperature is lowered, water is added, and emulsification is carried out to obtain a waterborne polyurethane acrylate emulsion;

[0008] Step (2), the waterborne polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion. The first emulsion, an initiator, oxazolidinone acrylate, gamma-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate and styrene are mixed and reacted. After the reaction is completed, the second emulsion is slowly added, and the reaction is continued. After the reaction is completed, a high-temperature-resistant waterproof coating is obtained.

[0009] Preferably, in the step (1), the mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, perfluoro chain extender, N-(4-hydroxyphenyl) maleimide is 2-3:1.1-1.3:0.05-0.1:20-22:60-65:10-20:2-3:2-3:1-2.

[0010] Preferably, in the step (1), the reaction conditions are: reacting for 4-5 h at a temperature of 100-110°C in a nitrogen atmosphere; the continued reaction conditions are: continuing to react for 2-3 h at a temperature of 70-80°C in a nitrogen atmosphere; and the re-reaction conditions are: re-reacting for 1-2 h at a temperature of 70-80°C in a nitrogen atmosphere.

[0011] Preferably, in the step (1), the end-capping reaction conditions are: end-capping reaction for 1-2 h at a temperature of 50-60°C in a nitrogen atmosphere; and the neutralization conditions are: neutralization reaction for 0.5-1 h at a temperature of 40-50°C.

[0012] Preferably, in the step (1), the solid content of the aqueous polyurethane acrylate emulsion is 38-44%.

[0013] Preferably, in the step (1), the perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2-epoxypropane and ethanolamine at a molar ratio of 2-2.5:1, and then reacting for 8-9 h at a temperature of 105-115°C.

[0014] Preferably, the hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material in the step (1) is prepared by the following steps:

[0015] S11, uniformly mixing concentrated sulfuric acid and water, adding montmorillonite, and activating treatment; after the treatment is completed, filtering, washing, and drying to obtain acidified montmorillonite;

[0016] S12, mixing the acidified montmorillonite, ethanol, and water, ultrasonic dispersion, dropwise adding 3-mercaptopropyl trimethoxysilane, after the dropwise addition is completed, reacting, after the reaction is completed, filtering, washing, and drying to obtain mercapto-functionalized montmorillonite;

[0017] S13, uniformly mixing the hydroxyl-terminated liquid butyl nitrile rubber, the mercapto-functionalized montmorillonite, and dichloromethane, adding a photoinitiator, reacting, after the reaction is completed, removing the solvent dichloromethane by rotary evaporation, washing, and drying to obtain the hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material.

[0018] Preferably, in the step (1) of preparing the hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, in S11, the mass ratio of concentrated sulfuric acid, water and montmorillonite is 100:50-60:35-45, the concentrated sulfuric acid is 98wt% concentrated sulfuric acid; the activation condition is that the activation treatment is stirred at 85-95℃ for 3-4h.

[0019] Preferably, in the step (1) of preparing the hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, in S12, the mass ratio of acidified montmorillonite, ethanol, water and 3-mercaptopropyl trimethoxysilane is 1:20-25:20-25:0.8-1; the reaction condition is that the reaction is stirred at room temperature for 6-8h.

[0020] Preferably, in the step (1) of preparing the hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, in S13, the mass ratio of hydroxyl-terminated liquid butyl nitrile rubber, mercapto-functionalized montmorillonite, dichloromethane and photoinitiator is 10:4-5:40-50:0.4-0.5; the reaction condition is that the reaction is stirred at room temperature for 10-14h in the environment of ultraviolet lamp with wavelength of 365nm.

[0021] Preferably, the photoinitiator comprises α-hydroxyisobutyryl benzene.

[0022] Preferably, in the step (2), the mass ratio of the first emulsion, the second emulsion, the initiator, the oxazolidinone acrylate, the γ-methacryloyloxypropyl trimethoxysilane, the hexafluorobutyl methacrylate and the styrene is 30-40:65-75:2-3:20-25:1-2:5-10:3-5; the reaction condition is that the reaction is carried out at 60-70℃ for 0.5-1h; the second emulsion is added at 1.5-2h; the continuous reaction condition is that the reaction is continuously carried out at 65-75℃ for 3-4h.

[0023] Preferably, the initiator comprises azobis isobutyronitrile.

[0024] Preferably, the oxazolidinone acrylate in the step (2) is prepared by the following steps:

[0025] The neopentyl glycol diacrylate, the 3-(2-hydroxyethyl)-2-oxazolidinone and the potassium carbonate are mixed and reacted, after the reaction is completed, the temperature is lowered, filtered, the filtrate is taken and dried to obtain the oxazolidinone acrylate.

[0026] Preferably, in the preparation of the oxazolidinone acrylate in the step (2), the mass ratio of the neopentyl glycol diacrylate, the 3-(2-hydroxyethyl)-2-oxazolidinone and the potassium carbonate is 42-48:26-30:3.4-3.9; the reaction condition is that the reaction is carried out at 45-55℃ for 16-18h.

[0027] Preferably, the high-temperature-resistant waterproof coating is prepared by the preparation method of the high-temperature-resistant waterproof coating.

[0028] Compared with the prior art, the application has the following beneficial effects:

[0029] The application introduces 4-(4-hydroxyphenyl) phthalazine-1-ol, N-(4-hydroxyphenyl) maleimide and a full-fluorine chain extender into the water-based polyurethane acrylate, and then performs free radical polymerization on the obtained water-based polyurethane acrylate emulsion and acrylate monomers under the condition of an initiator, so that the crosslinking degree of the matrix material is improved, and the high-temperature-resistant waterproof coating is obtained.

[0030] The hydroxyl-terminated liquid butyl nitrile rubber is a liquid synthetic rubber with hydroxyl functional groups at both ends, which is prepared by copolymerization of butadiene and acrylonitrile, and has non-polar and strong polar segments in the molecular chain, and has excellent oil resistance, water resistance, aging resistance and bonding performance.

[0031] The application introduces 4-(4-hydroxyphenyl) phthalazine-1-ol, N-(4-hydroxyphenyl) maleimide and a full-fluorine chain extender into the water-based polyurethane acrylate, and then performs free radical polymerization on the obtained water-based polyurethane acrylate emulsion and acrylate monomers under the condition of an initiator, so that the crosslinking degree of the matrix material is improved, and the high-temperature-resistant waterproof coating is obtained.

[0032] Among them, the perfluorinated chain extender is prepared by the ring-opening reaction of 3-perfluorohexyl-1,2-epoxypropane and ethanolamine. Introducing it into the matrix material can improve the hydrophobicity of the material. 4-(4-hydroxyphenyl)phthalazine-1-ol has a rigid heterocyclic naphthalene biphenyl structure, and N-(4-hydroxyphenyl)maleimide contains hydroxyl and vinylimide rings. It can react with the terminal isocyanate group of polyurethane prepolymer and copolymerize with acrylate monomers. Introducing the two into the matrix can synergistically improve the high temperature resistance and mechanical properties of the material.

[0033] Among acrylate monomers, oxazolidinone acrylate contains an oxazolidinone heterocyclic structure and a carbon-carbon double bond. It is prepared by a Michael addition reaction between neopentyl glycol diacrylate and 3-(2-hydroxyethyl)-2-oxazolidinone via a carbon-carbon double bond and a hydroxyl group. Introducing it into the matrix material can further improve the material's heat resistance. γ-methacryloyloxypropyltrimethoxysilane, as a tackifier, can improve the adhesion of the coating. Hexafluorobutyl methacrylate, as a fluorinated compound, together with perfluorinated chain extenders, improves the waterproof and hydrophobic properties of the coating. Attached Figure Description

[0034] Figure 1 This is a process flow diagram for preparing the high-temperature resistant waterproof coating in this invention;

[0035] Figure 2 This is a bar chart showing the impact strength of the embodiments and comparative examples in the performance test of this invention;

[0036] Figure 3 This is a bar chart showing the water absorption rate of the embodiments and comparative examples in the performance test of this invention. Detailed Implementation

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0038] Example 1

[0039] This embodiment discloses a method for preparing a high-temperature resistant waterproof coating, including the following steps:

[0040] Step (1), diphenylmethane diisocyanate and N,N-dimethylformamide are mixed and dissolved at a mass ratio of 1:4, 4-(4-hydroxyphenyl) phthalazine-1-ol and a catalyst stannous octoate are added, and the reaction is carried out at 100℃ for 5h in a nitrogen atmosphere; after the reaction is completed, the temperature is lowered, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material and 2,2-dimethylol propionic acid are added, and the reaction is continued at 70℃ for 3h; after the reaction is completed, perfluoro chain extender is added, and the reaction is carried out again at 70℃ for 2h; after the reaction is completed, the end-capping agent N-(4-hydroxyphenyl) maleimide is added, and the end-capping reaction is carried out at 50℃ for 2h; after the end-capping reaction is completed, triethylamine is added, and the neutralization reaction is carried out at 40℃ for 1h; after neutralization to neutral, the temperature is lowered to room temperature, water is added, and the high-speed stirring dispersion emulsification is carried out for 1h to obtain a water-based polyurethane acrylate emulsion with a solid content of 38%;

[0041] The mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, perfluoro chain extender and N-(4-hydroxyphenyl) maleimide is 2:1.1:0.05:20:65:10:2:2:1;

[0042] The perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2-epoxypropane and ethanolamine at a molar ratio of 2:1, and then reacting at 105℃ for 9h;

[0043] The hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0044] S11, 98wt% concentrated sulfuric acid is uniformly mixed with water, and montmorillonite is added; the mass ratio of 98wt% concentrated sulfuric acid, water and montmorillonite is 100:55:40; stirring and activation treatment is carried out at 90℃ for 3.5h; after the treatment is completed, filtration is carried out, the filter cake is taken out, and the filter cake is washed to neutral with 7 times the mass of water; drying is carried out at 105℃ for 10h to obtain acidified montmorillonite;

[0045] S12, the acidified montmorillonite, ethanol and water are mixed and ultrasonically dispersed for 1.5h; 3-mercaptopropyl trimethoxysilane is added dropwise, the dropwise addition time is 15min, and the mass ratio of acidified montmorillonite, ethanol, water and 3-mercaptopropyl trimethoxysilane is 1:23:22:0.9; after the dropwise addition is completed, stirring reaction is carried out at room temperature for 7h; after the reaction is completed, filtration is carried out, the filter cake is taken out, and the filter cake is sequentially washed to neutral with 6 times the mass of ethanol and water; drying is carried out at 75℃ for 16h to obtain thiol-functionalized montmorillonite;

[0046] S13, the hydroxyl-terminated liquid nitrile rubber, mercapto-functionalized montmorillonite, dichloromethane are mixed and stirred uniformly, and the photoinitiator a-hydroxyisobutyrylbenzene is added. The mass ratio of the hydroxyl-terminated liquid nitrile rubber, the mercapto-functionalized montmorillonite, the dichloromethane, and the a-hydroxyisobutyrylbenzene is 10:4:40:0.4. The reaction is stirred for 10 hours at room temperature in an environment of an ultraviolet lamp with a wavelength of 365 nm. After the reaction is completed, the solvent dichloromethane is removed by rotary evaporation at a temperature of 20 DEG C to obtain a reaction product. The reaction product is washed with ethanol for three times with a mass of 5 times of the reaction product. The product is dried at a temperature of 50 DEG C for 24 hours to obtain a hydroxyl-terminated nitrile rubber / montmorillonite composite material.

[0047] Step (2), the aqueous polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion. The first emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, gamma-methacryloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene are mixed and reacted at a temperature of 60 DEG C for 1 hour. After the reaction is completed, the second emulsion is slowly added over a period of 1.5 hours. After the addition is completed, the reaction is continued at a temperature of 65 DEG C for 4 hours. After the reaction is completed, a high-temperature-resistant waterproof coating is obtained.

[0048] The mass ratio of the first emulsion, the second emulsion, the initiator azobisisobutyronitrile, the oxazolidinone acrylate, the gamma-methacryloxypropyltrimethoxysilane, the hexafluorobutyl methacrylate, and the styrene is 30:75:2:20:1:5:3.

[0049] The oxazolidinone acrylate is prepared by the following steps:

[0050] New pentaerythritol diacrylate, 3-(2-hydroxyethyl)-2-oxazolidinone, and potassium carbonate are mixed in a mass ratio of 45:28:3.6 and reacted at a temperature of 50 DEG C for 17 hours. After the reaction is completed, the temperature is lowered to room temperature, and the mixture is filtered. The filtrate is dried at a temperature of 55 DEG C for 16 hours to obtain the oxazolidinone acrylate.

[0051] Example 2

[0052] The embodiment discloses a preparation method of a high-temperature-resistant waterproof coating, which comprises the following steps:

[0053] Step (1), diphenylmethane diisocyanate and N,N-dimethylformamide are mixed and dissolved at a mass ratio of 1:4, 4-(4-hydroxyphenyl) phthalazine-1-ol and a catalyst stannous octoate are added, and the reaction is carried out at 100℃ for 4.5h in a nitrogen atmosphere. After the reaction is completed, the temperature is lowered, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material and 2,2-dimethylol propionic acid are added, and the reaction is continued at 70℃ for 2.5h. After the reaction is completed, perfluoro chain extender is added, and the reaction is carried out again at 70℃ for 1.5h. After the reaction is completed, the capping agent N-(4-hydroxyphenyl) maleimide is added, and the capping reaction is carried out at 50℃ for 1.5h. After the capping reaction is completed, triethylamine is added, and the neutralization reaction is carried out at 40℃ for 0.5h. After neutralization to neutral, the temperature is lowered to room temperature, water is added, and the high-speed stirring dispersion emulsification is carried out for 1h to obtain a water-based polyurethane acrylate emulsion with a solid content of 39%;

[0054] wherein the mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, perfluoro chain extender, N-(4-hydroxyphenyl) maleimide is 2.3:1.15:0.08:20.5:64:13:2.3:2.3:1.3;

[0055] The perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2-epoxypropane and ethanolamine at a molar ratio of 2.2:1, and then reacting at 105℃ for 8.5h;

[0056] The hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0057] The hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0058] Step (2), the aqueous polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion, the first emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, gamma-methacryloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene are mixed and reacted at a temperature of 65 DEG C for 0.5 h, after the reaction is completed, the second emulsion is slowly added, the adding time is 2 h, after the adding is completed, the reaction is continuously carried out at a temperature of 70 DEG C for 3 h, after the reaction is completed, a high-temperature-resistant waterproof coating is obtained;

[0059] The mass ratio of the first emulsion, the second emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, gamma-methacryloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene is 33:72:2.3:22:1.3:6:3.5; the preparation of oxazolidinone acrylate is the same as that in Embodiment 1.

[0060] Embodiment 3

[0061] The embodiment discloses a preparation method of a high-temperature-resistant waterproof coating, comprising the following steps:

[0062] Step (1), diphenylmethane diisocyanate and N,N-dimethylformamide are mixed and dissolved at a mass ratio of 1:4.5, 4-(4-hydroxyphenyl) phthalazine-1-ol and a catalyst stannous octoate are added, and the mixture is reacted at a temperature of 105 DEG C for 4.5 h in a nitrogen atmosphere, after the reaction is completed, the temperature is lowered, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, and 2,2-dimethylol propionic acid are added, and the mixture is continuously reacted at a temperature of 75 DEG C for 2.5 h, after the reaction is completed, perfluoro chain extender is added, and the mixture is again reacted at a temperature of 75 DEG C for 1.5 h, after the reaction is completed, a capping agent N-(4-hydroxyphenyl) maleimide is added, and the mixture is capped at a temperature of 55 DEG C for 1.5 h, after the capping reaction is completed, triethylamine is added, and the mixture is neutralized at a temperature of 45 DEG C for 0.5 h, after the neutralization is completed, the temperature is lowered to room temperature, and water is added, and the mixture is dispersed and emulsified at a high speed for 1 h to obtain an aqueous polyurethane acrylate emulsion with a solid content of 40%;

[0063] The mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, perfluoro chain extender, and N-(4-hydroxyphenyl) maleimide is 2.5:1.2:0.08:21:63:15:2.5:2.5:1.5.

[0064] The perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2-epoxypropane and ethanolamine at a molar ratio of 2.3:1 and reacting at a temperature of 110 DEG C for 8.5 h;

[0065] The end-hydroxyl butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0066] The end-hydroxyl liquid butyl nitrile rubber, the mercapto-functionalized montmorillonite and dichloromethane are mixed and stirred uniformly, and the photoinitiator α-hydroxyisobutyrylbenzene is added, and the mass ratio of the end-hydroxyl liquid butyl nitrile rubber, the mercapto-functionalized montmorillonite, dichloromethane and α-hydroxyisobutyrylbenzene is 10:4.5:45:0.45, and the reaction is stirred at room temperature in the environment of the ultraviolet lamp with the wavelength of 365 nm for 12 hours, and after the reaction is completed, the solvent dichloromethane is removed by rotary evaporation at the temperature of 25 ℃ to obtain a reaction product, and the reaction product is washed with ethanol with the mass of 6 times of the reaction product for three times, and is dried at the temperature of 55 ℃ for 22 hours to obtain the end-hydroxyl butyl nitrile rubber / montmorillonite composite material; wherein the preparation of the mercapto-functionalized montmorillonite is the same as that in Example 1.

[0067] Step (2), the aqueous polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion, the first emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate and styrene are mixed and reacted at the temperature of 65 ℃ for 0.5 hours, after the reaction is completed, the second emulsion is slowly added, the adding time is 2 hours, after the addition is completed, the reaction is continued at the temperature of 70 ℃ for 3.5 hours, and after the reaction is completed, the high-temperature-resistant waterproof coating is obtained.

[0068] The mass ratio of the first emulsion, the second emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate and styrene is 35:70:2.5:23:1.5:8:4; and the preparation of the oxazolidinone acrylate is the same as that in Example 1.

[0069] Example 4

[0070] The embodiment discloses a preparation method of a high-temperature-resistant waterproof coating, which comprises the following steps:

[0071] Step (1), diphenylmethane diisocyanate and N,N-dimethylformamide are mixed and dissolved at a mass ratio of 1:5, 4-(4-hydroxyphenyl) phthalazine-1-ol and a catalyst stannous octoate are added, and the reaction is carried out at 110°C for 4.5h in a nitrogen atmosphere. After the reaction is completed, the temperature is lowered, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material and 2,2-dimethylol propionic acid are added, and the reaction is continued at 80°C for 2.5h. After the reaction is completed, perfluoro chain extender is added, and the reaction is carried out again at 80°C for 1.5h. After the reaction is completed, the capping agent N-(4-hydroxyphenyl) maleimide is added, and the capping reaction is carried out at 60°C for 1.5h. After the capping reaction is completed, triethylamine is added, and the neutralization reaction is carried out at 50°C for 0.5h. After neutralization to neutral, the temperature is lowered to room temperature, water is added, and the high-speed stirring dispersion emulsification is carried out for 1h to obtain a water-based polyurethane acrylate emulsion with a solid content of 42%;

[0072] The mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, perfluoro chain extender, and N-(4-hydroxyphenyl) maleimide is 2.8:1.25:0.08:21.5:62:18:2.8:2.8:1.8;

[0073] The perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2-epoxypropane and ethanolamine at a molar ratio of 2.4:1, and then reacting at 115°C for 8.5h;

[0074] The hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0075] The hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0076] Step (2), the waterborne polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion, the first emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, gamma-methacryloxypropyl trimethoxysilane, hexafluorobutyl methacrylate and styrene are mixed, and reaction is carried out at a temperature of 70 DEG C for 0.5 h; after the reaction is completed, the second emulsion is slowly added, the adding time is 2 h, after the adding is completed, reaction is continuously carried out at a temperature of 75 DEG C for 3.5 h; after the reaction is completed, a high-temperature-resistant waterproof coating is obtained;

[0077] The mass ratio of the first emulsion, the second emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, gamma-methacryloxypropyl trimethoxysilane, hexafluorobutyl methacrylate and styrene is 38:67:2.8:24:1.8:9:4.5; the preparation of oxazolidinone acrylate is the same as that in Embodiment 1.

[0078] Embodiment 5

[0079] The embodiment discloses a preparation method of a high-temperature-resistant waterproof coating, comprising the following steps:

[0080] Step (1), diphenylmethane diisocyanate and N,N-dimethylformamide are mixed and dissolved at a mass ratio of 1:5, 4-(4-hydroxyphenyl) phthalazine-1-ol and a catalyst stannous octoate are added, reaction is carried out at a temperature of 110 DEG C for 4 h in a nitrogen atmosphere, after the reaction is completed, cooling is carried out, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material and 2,2-dimethylol propionic acid are added, and reaction is continuously carried out at a temperature of 80 DEG C for 2 h, after the reaction is completed, perfluoro chain extender is added, and reaction is again carried out at a temperature of 80 DEG C for 1 h, after the reaction is completed, capping agent N-(4-hydroxyphenyl) maleimide is added, capping reaction is carried out at a temperature of 60 DEG C for 1 h, after the capping reaction is completed, triethylamine is added, and neutralization reaction is carried out at a temperature of 50 DEG C for 0.5 h, after neutralization to neutral, cooling is carried out to room temperature, water is added, and high-speed stirring dispersion emulsification is carried out for 1.5 h, to obtain a waterborne polyurethane acrylate emulsion with a solid content of 44%;

[0081] The mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, perfluoro chain extender and N-(4-hydroxyphenyl) maleimide is 3:1.3:0.1:22:60:20:3:3:2.

[0082] The perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2-epoxypropane and ethanolamine at a molar ratio of 2.5:1, and then carrying out reaction at a temperature of 115 DEG C for 8 h;

[0083] The hydroxyl-terminated nitrile butadiene rubber / montmorillonite composite material is prepared by the following steps:

[0084] Hydroxyl-terminated liquid nitrile butadiene rubber, mercapto-functionalized montmorillonite, and dichloromethane were mixed and stirred until homogeneous. Then, α-hydroxyisobutyroylbenzene, a photoinitiator, was added. The mass ratio of hydroxyl-terminated liquid nitrile butadiene rubber, mercapto-functionalized montmorillonite, dichloromethane, and α-hydroxyisobutyroylbenzene was 10:5:50:0.5. The mixture was stirred and reacted for 14 hours at room temperature under a 365 nm UV lamp. After the reaction, the solvent dichloromethane was removed by rotary evaporation at 30 °C to obtain the reaction product. The product was washed three times with ethanol at 8 times its mass, and then dried at 60 °C for 20 hours to obtain the hydroxyl-terminated nitrile butadiene rubber / montmorillonite composite material. The preparation of the mercapto-functionalized montmorillonite was the same as in Example 1.

[0085] Step (2): Divide the waterborne polyurethane acrylate emulsion into a first emulsion and a second emulsion. Mix the first emulsion, initiator azobisisobutyronitrile, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene. React at 70°C for 0.5 h. After the reaction is complete, slowly add the second emulsion over 2 h. After the addition is complete, continue the reaction at 75°C for 3 h. After the reaction is complete, a high-temperature resistant waterproof coating is obtained.

[0086] The mass ratio of the first emulsion, the second emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene was 40:65:3:25:2:10:5; the preparation of oxazolidinone acrylate was the same as in Example 1.

[0087] Comparative Example 1

[0088] This comparative example discloses a method for preparing a coating, comprising the following steps:

[0089] Step (1): Diphenylmethane diisocyanate and N,N-dimethylformamide were mixed and dissolved in a mass ratio of 1:4. 4-(4-hydroxyphenyl)phthalazine-1-ol and stannous octoate catalyst were added. The mixture was reacted at 100°C for 5 hours in a nitrogen atmosphere. After the reaction was completed, the temperature was lowered and isophorone diisocyanate, polytetrahydrofuran ether diol and 2,2-dimethylolpropionic acid were added. The mixture was reacted at 70°C for 3 hours. After the reaction was completed, perfluorinated chain extender was added and the mixture was reacted again at 70°C for 2 hours. After the reaction was completed, N-(4-hydroxyphenyl)maleimide end-capping agent was added and the mixture was end-capped at 50°C for 2 hours. After the end-capping reaction was completed, triethylamine was added and the mixture was neutralized at 40°C for 1 hour. After neutralization, the mixture was cooled to room temperature and water was added. The mixture was dispersed and emulsified by high-speed stirring for 1 hour to obtain an aqueous polyurethane acrylate emulsion with a solid content of 38%.

[0090] wherein the mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl) phthalazin-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether glycol, 2,2-dimethylol propionic acid, perfluoro chain extender, N-(4-hydroxyphenyl) maleimide is 2:1.1:0.05:20:75:2:2:1;

[0091] The perfluoro chain extender is prepared by mixing 3-perfluoro-n-hexyl-1,2- propylene oxide and ethanolamine at a molar ratio of 2:1, and then reacting at a temperature of 105°C for 9h;

[0092] Step (2), the aqueous polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion, the first emulsion, initiator azobisisobutyronitrile, methyl methacrylate, gamma-methacryloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene are mixed and reacted at a temperature of 60°C for 1h, after the reaction is completed, the second emulsion is slowly added, the addition time is 1.5h, after the addition is completed, the reaction is continued at a temperature of 65°C for 4h, after the reaction is completed, a coating is obtained;

[0093] wherein the mass ratio of the first emulsion, the second emulsion, initiator azobisisobutyronitrile, methyl methacrylate, gamma-methacryloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene is 30:75:2:20:1:5:3.

[0094] Comparative Example 2

[0095] This comparative example discloses a preparation method of a coating, comprising the following steps:

[0096] Step (1), diphenylmethane diisocyanate is mixed and dissolved with N,N- dimethylformamide at a mass ratio of 1:4, 4-(4-hydroxyphenyl) phthalazin-1-ol and catalyst stannous octoate are added, and the reaction is carried out at a temperature of 100°C for 5h in a nitrogen atmosphere, after the reaction is completed, the temperature is lowered, isophorone diisocyanate, polytetrahydrofuran ether glycol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, and 2,2-dimethylol propionic acid are added, and the reaction is continued at a temperature of 70°C for 3h, after the reaction is completed, 1,4-ethanediol is added, and the reaction is carried out again at a temperature of 70°C for 2h, after the reaction is completed, capping agent N-(4-hydroxyphenyl) maleimide is added, and capping reaction is carried out at a temperature of 50°C for 2h, after the capping reaction is completed, triethylamine is added, and neutralization reaction is carried out at a temperature of 40°C for 1h, after neutralization to neutral, the temperature is lowered to room temperature, water is added, and high-speed stirring dispersion emulsification is carried out for 1h, to obtain an aqueous polyurethane acrylate emulsion with a solid content of 38%;

[0097] The mass ratio of diphenyl methane diisocyanate, 4-(4-hydroxyphenyl) phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material, 2,2-dimethylol propionic acid, 1,4-ethylene glycol, and N-(4-hydroxyphenyl) maleimide is 2:1.1:0.05:20:65:10:2:2:1.

[0098] The hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material is prepared by the following steps:

[0099] The hydroxyl-terminated liquid butyl nitrile rubber, thiol-functionalized montmorillonite, and dichloromethane are uniformly mixed and stirred, and the photoinitiator α-hydroxyisobutyrylbenzene is added. The mass ratio of the hydroxyl-terminated liquid butyl nitrile rubber, thiol-functionalized montmorillonite, dichloromethane, and α-hydroxyisobutyrylbenzene is 10:4:40:0.4. The reaction is stirred for 10 hours at room temperature in an ultraviolet lamp environment with a wavelength of 365 nm. After the reaction is completed, the solvent dichloromethane is removed by rotary evaporation at a temperature of 20°C to obtain a reaction product. The reaction product is washed with 5 times the mass of ethanol three times, and then dried at a temperature of 50°C for 24 hours to obtain the hydroxyl-terminated butyl nitrile rubber / montmorillonite composite material. The preparation of the thiol-functionalized montmorillonite is the same as in Example 1.

[0100] Step (2), the aqueous polyurethane acrylate emulsion is divided into a first emulsion and a second emulsion. The first emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, methyl methacrylate, and styrene are mixed and reacted at a temperature of 60°C for 1 hour. After the reaction is completed, the second emulsion is slowly added over a period of 1.5 hours. After the addition is completed, the reaction is continued at a temperature of 65°C for 4 hours. After the reaction is completed, the coating is obtained.

[0101] The mass ratio of the first emulsion, the second emulsion, the initiator azobisisobutyronitrile, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, methyl methacrylate, and styrene is 30:75:2:20:1:5:3. The preparation of the oxazolidinone acrylate is the same as in Example 1.

[0102] In the above examples and comparative examples: 4-(4-hydroxyphenyl) phthalazine-1-ol was from Chongqing Futeng Pharmaceutical Co., Ltd., CAS No.: 152594-70-2; polytetrahydrofuran ether diol was from Shanghai Aladdin Biochemical Technology Co., Ltd., Mn = 2900; N-(4-hydroxyphenyl) maleimide was from Shanghai Maikelin Biochemical Technology Co., Ltd., CAS No.: 7300-91-6; 3-perfluoro-n-hexyl-1,2-epoxypropane was from Wuhan Kemik Biological Medicine Technology Co., Ltd., CAS No.: 38565-52-5; montmorillonite was from Zhejiang Linaqian Bentonite Chemical Co., Ltd., product name sodium-based montmorillonite, particle size 50 μm; 3-mercaptopropyl trimethoxysilane was from Alfa Aesar Company, CAS No.: 4420-74-0; hydroxyl-terminated liquid butyl nitrile rubber was from Zibo Qilong Chemical Co., Ltd., product name hydroxyl-terminated polybutadiene acrylonitrile HTBN, hydroxyl value 0.62 mmol / g, number average molecular weight 2000; γ-methacryloyloxypropyl trimethoxysilane was from Hangzhou Jessica Chemical Co., Ltd., product name silane coupling agent KH-570; hexafluorobutyl methacrylate was from Wuhan Lanna White Pharmaceutical Chemical Co., Ltd., CAS No.: 36405-47-7; neopentyl glycol diacrylate was from Guangdong Fangxin Biological Technology Co., Ltd., CAS No.: 2223-82-7; 3-(2-hydroxyethyl)-2-oxazolidinone was from Xi'an Qiyue Biological Technology Co., Ltd., CAS No.: 3356-88-5.

[0103] Test Example

[0104] The coatings prepared in the above examples and comparative examples were tested for performance, and the specific test results are shown in Table 1:

[0105] Table 1

[0106]

[0107]

[0108] The detection of each index in Table 1 was respectively based on the following standards: the adhesion was determined with reference to GB / T1720-1989 “Paint Film Adhesion Test Method”; the impact strength was determined with reference to GB / T1732-2020 “Paint Film Impact Resistance Test Method”; the water absorption was determined with reference to HGT3344-1985 “Paint Film Water Absorption Test Method”; the heat resistance was indicated by the thermal weight loss temperature and the film surface phenomenon, wherein the thermal weight loss temperature was determined by STA449F3 simultaneous thermal analyzer in nitrogen atmosphere, the test temperature was 50-600℃, the heating rate was 20K / min, and the weight loss rate was 5%; the film surface phenomenon was determined by observing the film surface phenomenon after the coating film of the examples and comparative examples was dried and then treated at a temperature of 300℃ for a certain time.

[0109] According to the test results of Table 1, it can be seen that the coating prepared by the application has excellent high-temperature-resistant waterproof performance and good mechanical performance.

[0110] In the application, the hydroxyl-terminated liquid nitrile rubber has excellent oil resistance, water resistance, aging resistance and bonding performance, and can improve the mechanical performance, water resistance and bonding performance of the coating; the hydroxyl-terminated nitrile rubber / montmorillonite composite material in the application can participate in the polymerization reaction of the waterborne polyurethane acrylate as a polyhydroxy polymer, thereby improving the dispersibility and compatibility of the montmorillonite in the waterborne polyurethane acrylate matrix, and the lamellar structure of the montmorillonite can be uniformly dispersed in the matrix, which has a certain shielding effect on water and heat, can delay the aging and chain scission of the polyurethane acrylate molecular chain, and further improves the heat-resistant and waterproof performance of the matrix.

[0111] 4-(4-hydroxyphenyl)phthalazine-1-ol has a rigid heterocyclic heteronaphthalene biphenyl structure, and N-(4-hydroxyphenyl)maleimide contains a vinyl imide ring, and the introduction of the two into the matrix can synergistically improve the high-temperature resistance and mechanical performance of the material; among the acrylate monomers, oxazolidinone acrylate contains an oxazolidinone heterocyclic structure and a carbon-carbon double bond, and the introduction of the oxazolidinone acrylate into the matrix material can further improve the heat resistance of the material; gamma-methacryloyloxypropyl trimethoxysilane as an adhesion promoter can improve the adhesion performance of the coating; methyl hexafluorobutyl acrylate as a fluorine-containing compound, together with the perfluoro chain extender, improves the waterproof and hydrophobic performance of the coating.

[0112] In Comparative Example 1, the hydroxyl-terminated nitrile rubber / montmorillonite composite material is not added, the oxazolidinone acrylate is replaced by methyl methacrylate, the lamellar structure of the montmorillonite is lacking, which cannot improve the heat resistance and waterproof performance of the coating, and the hydroxyl-terminated nitrile rubber cannot improve the adhesion of the coating; the oxazolidinone acrylate is lacking, which cannot improve the heat resistance of the coating, so the adhesion, mechanical performance, heat resistance and waterproof performance of the coating of Comparative Example 1 are all reduced.

[0113] In Comparative Example 2, the perfluoro chain extender is replaced by 1,4-ethanediol, and the methyl hexafluorobutyl acrylate is replaced by methyl methacrylate, and the fluorine-containing compound is lacking, which cannot improve the hydrophobic performance of the coating, so the waterproof performance of Comparative Example 2 is reduced.

[0114] Although embodiments of the application have been shown and described, it is to be understood that the application is not limited to these embodiments. Since modifications, equivalents, replacements, and variations of these embodiments can be understood by those of ordinary skill in the art without departing from the principles and spirits of the application, the scope of the application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a high-temperature resistant waterproof coating, characterized in that, Includes the following steps: Step (1): Diphenylmethane diisocyanate and N,N-dimethylformamide are mixed and dissolved. 4-(4-hydroxyphenyl)phthalazine-1-ol and stannous octoate are added and reacted. After the reaction is completed, the temperature is lowered and isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butadiene nitrile rubber / montmorillonite composite material and 2,2-dimethylolpropionic acid are added and the reaction is continued. After the reaction is completed, perfluorinated chain extender is added and the reaction is repeated. After the reaction is completed, N-(4-hydroxyphenyl)maleimide is added for end-capping reaction. After the reaction is completed, triethylamine is added for neutralization. After neutralization, the temperature is lowered and water is added for emulsification to obtain waterborne polyurethane acrylate emulsion. Step (2): Divide the waterborne polyurethane acrylate emulsion into a first emulsion and a second emulsion. Mix the first emulsion, initiator, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene and react. After the reaction is completed, slowly add the second emulsion. After the addition is complete, continue the reaction. After the reaction is completed, a high-temperature resistant waterproof coating is obtained.

2. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, In step (1), the mass ratio of diphenylmethane diisocyanate, 4-(4-hydroxyphenyl)phthalazine-1-ol, stannous octoate, isophorone diisocyanate, polytetrahydrofuran ether diol, hydroxyl-terminated butadiene-acrylonitrile rubber / montmorillonite composite material, 2,2-dimethylolpropionic acid, perfluorinated chain extender, and N-(4-hydroxyphenyl)maleimide is 2-3:1.1-1.3:0.05-0.1:20-22:60-65:10-20:2-3:2-3:1-2; the solid content of the waterborne polyurethane acrylate emulsion is 38-44%.

3. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, In step (1), the reaction conditions are: reaction at 100-110℃ for 4-5 hours in a nitrogen atmosphere; the continued reaction conditions are: reaction at 70-80℃ for 2-3 hours in a nitrogen atmosphere; the second reaction conditions are: reaction at 70-80℃ for 1-2 hours in a nitrogen atmosphere; the end-capping reaction conditions are: end-capping reaction at 50-60℃ for 1-2 hours in a nitrogen atmosphere; and the neutralization conditions are: neutralization reaction at 40-50℃ for 0.5-1 hours.

4. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, In step (1), the perfluorinated chain extender is prepared by mixing 3-perfluorohexyl-1,2-epoxypropane and ethanolamine in a molar ratio of 2-2.5:1 and reacting them at 105-115℃ for 8-9 hours.

5. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, The hydroxyl-terminated butadiene-acrylonitrile rubber / montmorillonite composite material in step (1) is prepared by the following steps: S11. Mix concentrated sulfuric acid with water until homogeneous, add montmorillonite, and activate the mixture. After the activation process, filter, wash, and dry to obtain acidified montmorillonite. S12. Mix acidified montmorillonite, ethanol and water, disperse by ultrasonication, add 3-mercaptopropyltrimethoxysilane dropwise, and after the addition is complete, react. After the reaction is complete, filter, wash and dry to obtain mercaptofunctionalized montmorillonite. S13. Hydroxyl-terminated liquid nitrile butadiene rubber, mercaptofunctionalized montmorillonite, and dichloromethane are mixed and stirred evenly. A photoinitiator is added, and the reaction is carried out. After the reaction is completed, the solvent dichloromethane is removed by rotary evaporation. The mixture is washed and dried to obtain a hydroxyl-terminated nitrile butadiene rubber / montmorillonite composite material.

6. The method for preparing a high-temperature resistant waterproof coating according to claim 5, characterized in that, When preparing the hydroxyl-terminated butadiene nitrile rubber / montmorillonite composite material, in S11 the mass ratio of concentrated sulfuric acid, water and montmorillonite is 100:50-60:35-45, and the concentrated sulfuric acid is 98wt% concentrated sulfuric acid; the activation conditions are: stirring and activating at 85-95℃ for 3-4 hours. In S12: the mass ratio of acidified montmorillonite, ethanol, water, and 3-mercaptopropyltrimethoxysilane is 1:20-25:20-25:0.8-1; the reaction conditions are: stirring at room temperature for 6-8 hours. In S13: the mass ratio of hydroxyl-terminated liquid nitrile rubber, mercaptofunctionalized montmorillonite, dichloromethane, and photoinitiator is 10:4-5:40-50:0.4-0.5; the reaction conditions are: stirring at room temperature under a 365nm ultraviolet lamp for 10-14 hours.

7. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, In step (2), the mass ratio of the first emulsion, the second emulsion, the initiator, oxazolidinone acrylate, γ-methacryloyloxypropyltrimethoxysilane, hexafluorobutyl methacrylate, and styrene is 30-40:65-75:2-3:20-25:1-2:5-10:3-5.

8. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, In step (2), the reaction conditions are: reacting at 60-70℃ for 0.5-1h; the second emulsion is added at 1.5-2h; and the reaction continues at 65-75℃ for 3-4h.

9. The method for preparing a high-temperature resistant waterproof coating according to claim 1, characterized in that, The oxazolidinone acrylate in step (2) is prepared by the following steps: Neopentyl glycol diacrylate, 3-(2-hydroxyethyl)-2-oxazolidinone, and potassium carbonate were mixed and reacted. After the reaction was completed, the mixture was cooled, filtered, and the filtrate was collected and dried to obtain oxazolidinone acrylate. The mass ratio of neopentyl glycol diacrylate, 3-(2-hydroxyethyl)-2-oxazolidinone, and potassium carbonate is 42-48:26-30:3.4-3.9; the reaction conditions are: reaction at 45-55℃ for 16-18 hours.

10. A high-temperature resistant waterproof coating prepared by the method for preparing a high-temperature resistant waterproof coating as described in any one of claims 1-9.

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