High-performance coating and color steel plate prepared thereby

Abstract

The application belongs to the technical field of paint, and particularly relates to high-performance paint and a color steel plate prepared by the same. The paint comprises the following components in parts by weight: 120-150 parts of water-based polyurethane dispersion liquid, 5-15 parts of long-chain fluorine-containing silane coupling agent modified graphene, 10-15 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotube, 1-4 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microsphere, 1-8 parts of additive, and 50-100 parts of solvent. The two-dimensional sheet-shaped modified graphene, one-dimensional linear modified carbon nanotube and zero-dimensional modified hollow glass microsphere are added in the water-based polyurethane to construct a three-dimensional space structure. The micro-nano structure is constructed on the surface of the coating through the compounding of the point, line and surface fillers, so that the hydrophobic performance of the coating is improved. The hollow glass microsphere has a low density, which can promote the dispersion of the components and is beneficial to the construction of the three-dimensional micro-nano rough structure, so that the coating realizes the super-hydrophobic performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of coatings, and particularly relates to a high-performance coating and a color steel plate prepared therefrom. BACKGROUND

[0002] Inspired by the "lotus effect", people found that super-hydrophobic surfaces have good self-cleaning, oil-water separation, anti-fogging and other characteristics, so super-hydrophobic materials have attracted much attention in recent years. At present, the most common way to construct super-hydrophobic surfaces is to use super-hydrophobic coatings. The main preparation method of super-hydrophobic coatings at present is sol-gel method, that is, nano-particles with certain chain length and particle size are generated through self-hydrolysis condensation reaction, and then the nano-particles are modified by using low surface energy substances. The characteristics of this preparation method are that the synthesis process of nano-particles is controllable, the modification degree is controllable and the raw materials are widely available. The prepared coating is coated on the surface of the material by dipping, spraying and other methods. When the preparation process parameters of super-hydrophobic coatings are determined, the performance is directly determined by the coating process. The commonly used coating process at present is spraying, which has the advantages of rough structure and good hydrophobic effect. The disadvantages are that the operation is difficult, many equipments are needed, and the parameters such as air pressure, gas flow rate and atomization level of the spray gun have certain requirements in the spraying process, which is easy to cause uneven spraying. Moreover, the surface of the coating obtained by spraying is rougher than that of dipping, so the transparency of the material is poor. Compared with spraying, dipping is more operable and practical. Because the coating obtained by dipping is more uniform, and for complex devices, internal cavities and gaps, dipping is the only feasible method. In addition, the methods for preparing super-hydrophobic coatings also include etching, electrospinning, electrodeposition and hydrothermal method, but many of these preparation methods have complex process, high manufacturing cost, and the prepared coating has poor wear resistance and low adhesion to the substrate, which limits its application range.

[0003] At present, the research on super-hydrophobic surfaces at home and abroad mainly focuses on the preparation of super-hydrophobic surfaces using volatile organic compounds as solvents, while the related technology of green and environmentally friendly water-based super-hydrophobic coatings using water as solvent is less. The main reason is that the hydrophilic groups left inside and on the surface of the coating after water evaporation will affect the hydrophobic stability and durability of the water-based super-hydrophobic coating, limiting the practical application of the water-based super-hydrophobic coating.

[0004] Waterborne polyurethane is a booming waterborne polymer material, which has the advantages of non-toxicity, environmental protection, safety, etc., and is an ideal raw material for preparing environmentally friendly products. The series of patents CN119752303A and CN119684886A applied by the technical cooperation enterprise of the company, Zibo Jiayue Board Co., Ltd., prepared a waterborne polyurethane coating with high adhesion and high corrosion resistance by compounding graphene and particulate inorganic nano filler. However, it has high hydrophilicity and does not have super hydrophobic effect. Later, the company prepared an organic silicon polyurethane composite material to improve the hydrophobic performance of the coating. However, the preparation process requires the use of a large amount of organic solvent, which not only pollutes seriously, but also has limited improvement in hydrophobic performance.

[0005] Currently, the technology of preparing hydrophobic waterborne polyurethane coating through chemical modification is quite mature, but its application in the preparation of super hydrophobic coating is less studied, mainly focusing on the preparation of silicon-containing or fluorine-containing polyurethane using organic silicon or fluorine-containing monomers, which has complex process, high cost and narrow industrial application range. SUMMARY

[0006] The purpose of the present application is to overcome the problems of high cost, complicated preparation process and difficulty in industrial scale-up of super hydrophobic materials in the prior art, and to provide a waterborne polyurethane composite coating with super hydrophobic performance and a preparation method thereof, which aims to prepare a super hydrophobic composite material with good corrosion resistance by a simpler process.

[0007] To achieve the above purpose, the present application provides a high-performance coating, which comprises the following components by weight:

[0008] Waterborne polyurethane dispersion 120-150 parts, long-chain fluorine-containing silane coupling agent modified graphene 5-15 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 10-15 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 1-4 parts, auxiliary agent 1-8 parts, solvent 50-100 parts.

[0009] There are two main ideas for preparing super-hydrophobic surfaces, one is to make rough structure on the surface of low surface energy material, and the other is to modify the rough surface with low surface energy material. In the traditional method of constructing super-hydrophobic surface, single nano-particle is usually used to construct micro-nano rough structure, and the surface roughness of single nano-particle on the coating surface is limited, and it is easy to be removed by mechanical wear, which directly makes the coating lose the super-hydrophobic property, which causes great obstacle to the application of super-hydrophobic coating. Improving the microstructure of the coating surface can effectively increase the durability of the super-hydrophobic surface. Therefore, the long-chain fluorine-containing silane coupling agent modified two-dimensional graphene, long-chain fluorine-containing silane coupling agent modified one-dimensional linear carbon nanotube and long-chain fluorine-containing silane coupling agent modified zero-dimensional granular hollow glass microspheres are added in the water-based polyurethane to construct three-dimensional space structure. The micro-nano structure is successfully constructed on the surface of the coating by the compounding of point, line and plane fillers. Moreover, the nano-scale wrinkles are spontaneously formed in the space of graphene, and the micro-nano convex structure similar to the surface of lotus leaf is formed on the surface after the fibrous carbon nanotube and micrometer-sized particles are dried, so as to increase the surface roughness of the composite coating as a whole. In addition, the pore structure appears between the fibers and particles on the surface of the coating, and air layer can be embedded in the pores to further improve the hydrophobic property. The micro-nano structure plays a super-hydrophobic role, and the microstructure can protect the nanostructure from being damaged, so that the coating has good stability.

[0010] The introduction of long-chain fluorine-containing silane coupling agent not only reduces the surface energy of graphene, carbon nanotube and hollow glass microsphere, but also helps the mutual contact among graphene, carbon nanotube and hollow glass microsphere due to the mutual entanglement of long-chain structure, so as to avoid the agglomeration of single material and improve the dispersion performance, which is beneficial to improve the corrosion resistance of the coating. The hollow glass microspheres are selected in the present application because they have low density and better suspension characteristics in the water-based polyurethane coating, so as to promote the dispersion of graphene and carbon nanotube, and to construct three-dimensional micro-nano rough structure on the surface of the coating by the zero-dimensional particles, one-dimensional carbon nanotube and two-dimensional graphene. The structure is very similar to the structure of lotus leaf, so the coating has lotus effect and can achieve self-cleaning effect. When the coating is exposed to air, the rough structure is filled with a large amount of air to form an air film, which can prevent direct contact with liquid and form a solid-air-water contact mode, so that the coating realizes super-hydrophobic property.

[0011] In an embodiment, the solid content of the water-based polyurethane dispersion is 40-80%.

[0012] In an embodiment, the long-chain fluorine-containing silane coupling agent modified graphene, long-chain fluorine-containing silane coupling agent modified carbon nanotube, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere are graphene, carbon nanotube, hollow glass microsphere modified by perfluorosilane coupling agent.

[0013] In an embodiment, the long-chain fluorine-containing silane coupling agent is one or more of perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltrichlorosilane.

[0014] In an embodiment, the graphene has a lateral size of 1-10 μm. In particular, the graphene is used in an amount of 5-10 parts. Graphene is a common nanoscale filler, which has a large aspect ratio. By using linear carbon nanotubes as the main body of the nanostructure, and using sheet graphene and spherical hollow microspheres to construct a micro-nano rough structure on the surface of the coating. An appropriate amount of graphene promotes the formation of micro-nano structures, and avoids excessive sheet graphene affecting the surface morphology of the coating.

[0015] In an embodiment, the carbon nanotube has a length of 10-50 μm. The diameter of the carbon nanotube is not particularly limited, and common 10-80 nm can be used.

[0016] In an embodiment, the hollow glass microsphere has a particle size of 2-50 μm. Compared with solid glass microspheres, hollow glass microspheres have a lower density, generally 0.20-0.60 g / cm 3 In the aqueous polyurethane coating, it has good dispersion performance, and can promote the dispersion of two-dimensional graphene and one-dimensional carbon nanotubes. The inventors found that if solid glass beads are used, due to their high density, they cannot promote the dispersion of graphene and carbon nanotubes, and cannot construct a three-dimensional micro-nano rough structure on the surface of the coating, and the contact angle can only reach about 123°, which cannot meet the performance requirements of superhydrophobicity. An appropriate amount of hollow glass microspheres can promote the dispersion of fillers, but when the amount exceeds a certain range, the increase of excessive inert fillers will increase the instability of the coating, which is not conducive to the formation of micro-nano structures on the surface of the coating, resulting in a decrease in the contact angle and a decrease in the hydrophobicity.

[0017] In an embodiment, the auxiliary agent is one or more of a anti-settling agent, a defoaming agent, a wetting dispersant, a leveling agent, a preservative, and an antibacterial agent.

[0018] In particular, the anti-settling agent is any one of fumed silica, organic bentonite, polyamide wax or polyethylene wax, modified urea. The defoaming agent is any one of fluorosilicon modified polysiloxane defoaming agent, polydimethylsiloxane defoaming agent. The wetting dispersant is any one of unsaturated polycarboxylic acid polymer, sodium polyacrylate, triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, polyacrylamide, gum gurjun or fatty acid polyethylene glycol ester. The leveling agent is any one of acrylic acid or fluorophosphate ester. The preservative is any one of LF-B20 preservative, isothiazolone derivative or n-octyl isothiazolinone.

[0019] In an embodiment, the solvent is deionized water.

[0020] In an embodiment, the preparation process of the long-chain fluorine-containing silane coupling agent modified graphene is as follows:

[0021] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acid is added to adjust the pH, and a mixed solution is obtained after hydrolysis at room temperature; the graphene is added into the mixed solution, stirred and reacted, and then filtered, washed and dried to obtain the long-chain fluorine-containing silane coupling agent modified graphene.

[0022] In an embodiment, the mass ratio of the long-chain fluorine-containing silane coupling agent to the graphene is (0.05-0.4):1. Specifically, it can be 0.05:1, 0.1:1, 0.2:1, 0.3:1 or 0.4:1. Further, it is 0.1:1 or 0.2:1.

[0023] In an embodiment, the preparation process of the long-chain fluorine-containing silane coupling agent modified carbon nanotube is as follows:

[0024] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acid is added to adjust the pH, and a mixed solution is obtained after hydrolysis at room temperature; the carbon nanotube is added into the mixed solution, stirred and reacted, and then filtered, washed and dried to obtain the long-chain fluorine-containing silane coupling agent modified carbon nanotube.

[0025] In an embodiment, the mass ratio of the long-chain fluorine-containing silane coupling agent to the carbon nanotube is (0.05-0.4):1. Specifically, it can be 0.05:1, 0.1:1, 0.2:1, 0.3:1 or 0.4:1. Further, it is 0.1:1 or 0.2:1.

[0026] In an embodiment, the preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows:

[0027] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, an acid is added to adjust the pH, and a mixed solution is obtained after hydrolysis at room temperature; the hollow glass microspheres are added into the mixed solution, stirred and reacted, and then filtered, washed, and dried to obtain the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres.

[0028] In an embodiment, the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is (0.05-0.4):1. Specifically, it can be 0.05:1, 0.1:1, 0.2:1, 0.3:1, or 0.4:1. Further, it can be 0.1:1 or 0.2:1. If the amount of the long-chain fluorine-containing silane coupling agent is too small, the modification of the hollow glass microspheres is not complete; however, if the amount of the long-chain fluorine-containing silane coupling agent is too large, the long-chain fluorine-containing silane coupling agent is prone to self-crosslinking after hydrolysis, resulting in poor dispersibility of the hollow glass microspheres.

[0029] In an embodiment, the acid is one or more of formic acid, acetic acid, citric acid, and lactic acid. The pH is 3-5.

[0030] In an embodiment, the hydrolysis time is 1-2 h. The stirring and reaction temperature is 45-55℃, and the reaction time is 4-8 h.

[0031] In an embodiment, the preparation method of the high-performance coating includes the following steps:

[0032] In an embodiment, the long-chain fluorine-containing silane coupling agent modified graphene, the long-chain fluorine-containing silane coupling agent modified carbon nanotube, the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, and the solvent are uniformly mixed, the water-based polyurethane dispersion liquid is added, stirred and dispersed, and then the additives are added and uniformly mixed again to obtain a high-performance coating.

[0033] On the other hand, the present application also provides a color steel plate, which is prepared by coating the high-performance coating on the surface of a color steel plate after cleaning treatment. The high-performance coating is coated on the surface of the color steel plate, improving the hydrophobicity and corrosion resistance of the color steel plate, and can be widely used in high-humidity and high-corrosion environments.

[0034] Beneficial effects: the addition of two-dimensional sheet-shaped graphene modified by long-chain fluorine-containing silane coupling agent, one-dimensional linear carbon nanotubes modified by long-chain fluorine-containing silane coupling agent and zero-dimensional particulate hollow glass microspheres modified by long-chain fluorine-containing silane coupling agent in the waterborne polyurethane constructs a three-dimensional space structure. Through the point, line and surface three kinds of filler compounding, the micro-nano structure is successfully constructed on the surface of the coating, and the hydrophobic performance of the coating is further improved. Among them, the introduction of long-chain fluorine-containing silane coupling agent not only reduces the surface energy of graphene, carbon nanotubes and hollow glass microspheres, but also helps the mutual contact among graphene, carbon nanotubes and hollow glass microspheres, avoids the agglomeration of single material, improves the dispersion performance, and is beneficial to improve the compactness and corrosion resistance of the coating. The hollow glass microspheres have lower density and better suspension properties in the waterborne polyurethane coating, which can promote the dispersion of graphene and carbon nanotubes, so that the zero-dimensional particles, one-dimensional carbon nanotubes and two-dimensional graphene construct a three-dimensional micro-nano rough structure on the surface of the coating, form a solid-air-water contact mode, and thus the coating realizes super-hydrophobic performance. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0036] In the following examples and comparative examples, the specific preparation process of long-chain fluorine-containing silane coupling agent modified graphene is as follows: the long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4, and a mixed solution is obtained after hydrolysis at room temperature for 1.3 h; the graphene with an average lateral size of 3 μm is added to the mixed solution, and the stirring reaction is carried out at 52℃ for 7 h, and then the long-chain fluorine-containing silane coupling agent modified graphene is obtained after filtration, washing and drying. The mass ratio of the long-chain fluorine-containing silane coupling agent to the graphene is 0.2:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane; and the volume ratio of ethanol to deionized water is 7:1.

[0037] In the following examples and comparative examples, the specific preparation process of long-chain fluorine-containing silane coupling agent modified carbon nanotubes is as follows: the long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.6 h; the carbon nanotubes with an average length of 30 μm are added to the mixed solution, and the stirring reaction is carried out at 50℃ for 6 h, and then the long-chain fluorine-containing silane coupling agent modified carbon nanotubes are obtained after filtration, washing and drying. The mass ratio of the long-chain fluorine-containing silane coupling agent to the carbon nanotubes is 0.25:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane; and the volume ratio of ethanol to deionized water is 7:1.

[0038] The coating preparation process in the following examples and comparative examples is as follows: the long-chain fluorine-containing silane coupling agent modified graphene, long-chain fluorine-containing silane coupling agent modified carbon nanotube, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere, and deionized water are uniformly mixed, then the water-based polyurethane dispersion liquid is added, stirred and dispersed, then the additives are added, and uniformly mixed again to obtain a high-performance coating. In Comparative Examples 1-3, the component with an amount of 0 is not added.

[0039] Subsequently, under the same conditions, the salt spray resistance of the high-performance coating prepared in the examples and comparative examples is tested according to GB / T 1771-2007, and the contact angle of the coating is tested by a contact angle measuring instrument.

[0040] Example 1

[0041] A high-performance coating comprises the following components by weight:

[0042] The water-based polyurethane dispersion liquid is 120 parts, the long-chain fluorine-containing silane coupling agent modified graphene is 5 parts, the long-chain fluorine-containing silane coupling agent modified carbon nanotube is 10 parts, the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is 1 part, BYK420 is 0.5 part, the sodium salt of polyacrylic acid is 0.5 part, the polydimethylsiloxane is 0.5 part, and the deionized water is 60 parts; the solid content of the water-based polyurethane dispersion liquid is 62%;

[0043] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows:

[0044] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1 h; the hollow glass microspheres with an average particle size of 15 μm are added to the mixed solution, and the reaction is stirred at 45°C for 8 h, then filtered, washed, and dried to obtain the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.1:1; the volume ratio of ethanol to deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating is 1420 h, and the contact angle is 155.2°.

[0045] Example 2

[0046] A high-performance coating comprises the following components by weight:

[0047] Water-based polyurethane dispersion 150 parts, long-chain fluorine-containing silane coupling agent modified graphene 10 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 15 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 4 parts, BYK420 2.5 parts, polyacrylic acid sodium salt 2.5 parts, polydimethylsiloxane 2.5 parts, deionized water 100 parts; the solid content of the water-based polyurethane dispersion is 62%;

[0048] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows:

[0049] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 2h; the average particle size of the hollow glass microspheres is 15μm, which is added to the mixed solution, and the reaction is stirred at 55℃ for 4h, then filtered, washed and dried to obtain long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.3:1; the volume ratio of ethanol to deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating reaches 1640h; the contact angle is 162.1°.

[0050] Example 3

[0051] A high-performance coating, comprising the following components by weight:

[0052] Water-based polyurethane dispersion 130 parts, long-chain fluorine-containing silane coupling agent modified graphene 15 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 12 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 2 parts, BYK420 1.5 parts, polyacrylic acid sodium salt 1.5 parts, polydimethylsiloxane 1.5 parts, deionized water 80 parts; the solid content of the water-based polyurethane dispersion is 62%;

[0053] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows:

[0054] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 2h; the average particle size of the hollow glass microspheres is 15μm, which is added to the mixed solution, and the reaction is stirred at 55℃ for 4h, then filtered, washed and dried to obtain long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.3:1; the volume ratio of ethanol to deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating reaches 1640h; the contact angle is 162.1°.

[0055] Example 4

[0056] A high-performance coating, comprising the following components by weight:

[0057] water-based polyurethane dispersion 125 parts, long-chain fluorine-containing silane coupling agent modified graphene 10 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 10 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 4 parts, BYK420 0.5 parts, polyacrylic acid sodium salt 2.5 parts, polydimethylsiloxane 0.5 parts, deionized water 100 parts; the solid content of the water-based polyurethane dispersion is 62%;

[0058] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is:

[0059] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and after hydrolysis at room temperature for 1h, a mixed solution is obtained; the average particle size of the hollow glass microspheres is 15μm, which is added to the mixed solution, and stirred at 45℃ for 4h, then filtered, washed and dried to obtain long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent and the hollow glass microspheres is 0.28:1; the volume ratio of ethanol and deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating reaches 1570h; the contact angle is 159.6°.

[0060] Example 5

[0061] A high-performance coating, comprising the following components by weight:

[0062] water-based polyurethane dispersion 130 parts, long-chain fluorine-containing silane coupling agent modified graphene 8 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 12 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 2 parts, BYK420 1.5 parts, polyacrylic acid sodium salt 1.5 parts, polydimethylsiloxane 1.5 parts, deionized water 80 parts; the solid content of the water-based polyurethane dispersion is 62%;

[0063] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is:

[0064] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.5 hours; the hollow glass microspheres with an average particle size of 15 μm are added into the mixed solution, and the reaction is stirred at 50℃ for 6 hours, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.05:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating reaches 1480 hours; and the contact angle is 156.8°.

[0065] Example 6

[0066] A high-performance coating comprises the following components by weight:

[0067] 130 parts of a water-based polyurethane dispersion, 6.5 parts of long-chain fluorine-containing silane coupling agent modified graphene, 12 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotubes, 2 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, 1 part of BYK420, 1 part of polyacrylic acid sodium salt, 1 part of polydimethylsiloxane, and 70 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0068] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres is as follows:

[0069] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.2 hours; the hollow glass microspheres with an average particle size of 15 μm are added into the mixed solution, and the reaction is stirred at 48℃ for 7 hours, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.15:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating reaches 1460 hours; and the contact angle is 157.1°.

[0070] Example 7

[0071] A high-performance coating comprises the following components by weight:

[0072] 130 parts of a water-based polyurethane dispersion, 6.5 parts of long-chain fluorine-containing silane coupling agent modified graphene, 12 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotubes, 2 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, 1 part of BYK420, 1 part of polyacrylic acid sodium salt, 1 part of polydimethylsiloxane, and 70 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0073] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres is as follows:

[0074] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.5 h; the hollow glass microspheres with an average particle size of 15 μm are added to the mixed solution, and the reaction is stirred at 50℃ for 6 h, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.4:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating is 1510 h, and the contact angle is 161.3°.

[0075] Example 8

[0076] A high-performance coating comprises the following components by weight:

[0077] 140 parts of a water-based polyurethane dispersion, 8.5 parts of long-chain fluorine-containing silane coupling agent modified graphene, 14 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotubes, 3 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, 2 parts of BYK420, 2 parts of polyacrylic acid sodium salt, 2 parts of polydimethylsiloxane, and 90 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0078] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres is as follows:

[0079] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.8 h; the hollow glass microspheres with an average particle size of 15 μm are added to the mixed solution, and the reaction is stirred at 52℃ for 5 h, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.25:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating is 1590 h, and the contact angle is 160.5°.

[0080] Example 9

[0081] A high-performance coating comprises the following components by weight:

[0082] Waterborne polyurethane dispersion 125 parts, long-chain fluorine-containing silane coupling agent modified graphene 7.5 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 13.5 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 1.5 parts, BYK420 1.8 parts, polyacrylic acid sodium salt 1 part, polydimethylsiloxane 1.7 parts, deionized water 80 parts; the solid content of the waterborne polyurethane dispersion is 62%;

[0083] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows:

[0084] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.8 h; the average particle size of the hollow glass microspheres is 15 μm, which is added to the mixed solution, and the reaction is stirred at 46℃ for 7.5 h, and then filtered, washed and dried to obtain the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.13:1; the volume ratio of ethanol to deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating is 1600 h; the contact angle is 161.6°.

[0085] Example 10

[0086] A high-performance coating, comprising the following components by weight:

[0087] Waterborne polyurethane dispersion 130 parts, long-chain fluorine-containing silane coupling agent modified graphene 8 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 12 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 2 parts, BYK420 1.5 parts, polyacrylic acid sodium salt 1.5 parts, polydimethylsiloxane 1.5 parts, deionized water 80 parts; the solid content of the waterborne polyurethane dispersion is 62%;

[0088] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows:

[0089] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.8 h; the average particle size of the hollow glass microspheres is 15 μm, which is added to the mixed solution, and the reaction is stirred at 46℃ for 7.5 h, and then filtered, washed and dried to obtain the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.13:1; the volume ratio of ethanol to deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating is 1600 h; the contact angle is 161.6°.

[0090] Comparative Example 1

[0091] A high-performance coating, comprising the following components by weight:

[0092] 130 parts of a water-based polyurethane dispersion, 0 parts of long-chain fluorine-containing silane coupling agent modified graphene, 18.9 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotube, 3.1 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microsphere, 1.5 parts of BYK420, 1.5 parts of polyacrylic acid sodium salt, 1.5 parts of polydimethylsiloxane, 80 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0093] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is:

[0094] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, and acetic acid is added to adjust the pH to 4.5. After hydrolysis at room temperature for 1.5 h, a mixed solution is obtained. The average particle size of the hollow glass microspheres is 15 μm. After stirring at 50℃ for 6 h, the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying. The mass ratio of the long-chain fluorine-containing silane coupling agent and the hollow glass microspheres is 0.2:1; the volume ratio of ethanol and deionized water is 7:1; the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. The salt spray resistance of the coating reaches 1010 h; the contact angle is 135.6°.

[0095] Comparative Example 2

[0096] A high-performance coating, comprising the following components by weight:

[0097] 130 parts of a water-based polyurethane dispersion, 0 parts of long-chain fluorine-containing silane coupling agent modified graphene, 18.9 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotube, 3.1 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microsphere, 1.5 parts of BYK420, 1.5 parts of polyacrylic acid sodium salt, 1.5 parts of polydimethylsiloxane, 80 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0098] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is:

[0099] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.5 hours; the hollow glass microspheres with an average particle size of 15 μm are added into the mixed solution, and the reaction is carried out at 50℃ for 6 hours under stirring, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.2:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. It is detected that the salt spray resistance of the coating reaches 1060 hours; and the contact angle is 138.8°.

[0100] Comparative Example 3

[0101] A high-performance coating comprises the following components by weight:

[0102] 130 parts of a water-based polyurethane dispersion, 8.8 parts of long-chain fluorine-containing silane coupling agent modified graphene, 13.2 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotubes, 0 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, 1.5 parts of BYK420, 1.5 parts of polyacrylic acid sodium salt, 1.5 parts of polydimethylsiloxane, and 80 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0103] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres is as follows:

[0104] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.5 hours; the hollow glass microspheres with an average particle size of 15 μm are added into the mixed solution, and the reaction is carried out at 50℃ for 6 hours under stirring, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.2:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. It is detected that the salt spray resistance of the coating reaches 1240 hours; and the contact angle is 131.2°.

[0105] Comparative Example 4

[0106] A high-performance coating comprises the following components by weight:

[0107] 130 parts of a water-based polyurethane dispersion, 8.8 parts of long-chain fluorine-containing silane coupling agent modified graphene, 13.2 parts of long-chain fluorine-containing silane coupling agent modified carbon nanotubes, 0 parts of long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, 1.5 parts of BYK420, 1.5 parts of polyacrylic acid sodium salt, 1.5 parts of polydimethylsiloxane, and 80 parts of deionized water; the solid content of the water-based polyurethane dispersion is 62%;

[0108] The preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres is as follows:

[0109] The long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acetic acid is added to adjust the pH to 4.5, and a mixed solution is obtained after hydrolysis at room temperature for 1.5 h; the hollow glass microspheres with an average particle size of 15 μm are added into the mixed solution, and the reaction is carried out at 50℃ for 6 h under stirring, and then the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres are obtained after filtration, washing and drying; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is 0.2:1; the volume ratio of ethanol to deionized water is 7:1; and the long-chain fluorine-containing silane coupling agent is perfluorodecyltrimethoxysilane. It is detected that the salt spray resistance of the coating reaches 1550 h, and the contact angle is 142.4°.

[0110] As can be seen from the above examples and comparative examples, the two-dimensional sheet-shaped graphene modified by the long-chain fluorine-containing silane coupling agent, the one-dimensional linear carbon nanotube modified by the long-chain fluorine-containing silane coupling agent, and the zero-dimensional particulate hollow glass microspheres modified by the long-chain fluorine-containing silane coupling agent are added in the water-based polyurethane to construct a three-dimensional space structure. The micro-nano structure is successfully constructed on the surface of the coating by the compounding of the three fillers of point, line and plane, and the introduction of the perfluorosilane coupling agent further reduces the surface energy of the rough surface. The micro-nano structure plays a super-hydrophobic role, and the micron structure can protect the nano structure from being damaged, so that the coating has good stability and improves the corrosion resistance. Compared with Example 10, Comparative Examples 1-3 respectively lack the long-chain fluorine-containing silane coupling agent modified graphene, the long-chain fluorine-containing silane coupling agent modified carbon nanotube, and the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres, and cannot form a micro-nano rough structure on the surface of the coating by the characteristics of the fillers themselves, and affect the dispersion of the fillers, reduce the compactness of the coating, and reduce the salt spray resistance and hydrophobicity. Although the salt spray resistance of Comparative Example 4 does not change much, the amount of the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres is too much, which increases the instability of the coating, is not conducive to the formation of the micro-nano structure on the surface of the coating, reduces the contact angle, and reduces the hydrophobicity.

[0111] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application belong to the scope of the claims of the present application and their equivalent technologies, the present application also intends to include these modifications and variations.

Claims

1. A high performance coating characterized by, The high-performance coating comprises the following components in parts by weight: water-based polyurethane dispersion 120-150 parts, long-chain fluorine-containing silane coupling agent modified graphene 5-15 parts, long-chain fluorine-containing silane coupling agent modified carbon nanotube 10-15 parts, long-chain fluorine-containing silane coupling agent modified hollow glass microsphere 1-4 parts, additive 1-8 parts, and solvent 50-100 parts; the long-chain fluorine-containing silane coupling agent is one or more of perfluorodecyltrichlorosilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltriethoxysilane, perfluorooctyltrimethoxysilane, and perfluorooctyltrichlorosilane; the preparation process of the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere is as follows: the long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acid is added to adjust the pH, and then a mixed solution is obtained after hydrolysis at room temperature; the hollow glass microspheres are added into the mixed solution, stirred and reacted, and then filtered, washed, and dried to obtain the long-chain fluorine-containing silane coupling agent modified hollow glass microspheres; the mass ratio of the long-chain fluorine-containing silane coupling agent to the hollow glass microspheres is (0.05-0.4):1; the preparation process of the long-chain fluorine-containing silane coupling agent modified graphene is as follows: the long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acid is added to adjust the pH, and then a mixed solution is obtained after hydrolysis at room temperature; the graphene is added into the mixed solution, stirred and reacted, and then filtered, washed, and dried to obtain the long-chain fluorine-containing silane coupling agent modified graphene; the mass ratio of the long-chain fluorine-containing silane coupling agent to the graphene is (0.05-0.4):1; the preparation process of the long-chain fluorine-containing silane coupling agent modified carbon nanotube is as follows: the long-chain fluorine-containing silane coupling agent is dispersed in a mixed solvent of ethanol and deionized water, acid is added to adjust the pH, and then a mixed solution is obtained after hydrolysis at room temperature; the carbon nanotube is added into the mixed solution, stirred and reacted, and then filtered, washed, and dried to obtain the long-chain fluorine-containing silane coupling agent modified carbon nanotube; the mass ratio of the long-chain fluorine-containing silane coupling agent to the carbon nanotube is (0.05-0.4):

1.

2. A high performance coating as claimed in claim 1, characterised in that, the additive is one or more of a sedimentation inhibitor, a defoaming agent, a wetting dispersant, a leveling agent, a preservative, and an antibacterial agent.

3. A high performance coating as claimed in claim 1, wherein, the solvent is deionized water.

4. A high performance coating as in claim 1, wherein, the acid is one or more of formic acid, acetic acid, citric acid, and lactic acid; and the pH is 3-5.

5. A high performance coating as in claim 1, wherein, the hydrolysis time is 1-2 h; the stirring and reaction temperature is 45-55℃, and the reaction time is 4-8 h.

6. A high performance coating as in claim 1, wherein, the preparation method of the high-performance coating comprises the following steps: the long-chain fluorine-containing silane coupling agent modified graphene, the long-chain fluorine-containing silane coupling agent modified carbon nanotube, the long-chain fluorine-containing silane coupling agent modified hollow glass microsphere, and the solvent are uniformly mixed, the water-based polyurethane dispersion is added, stirred and dispersed, then the additive is added, and the mixture is uniformly mixed again to obtain the high-performance coating.

7. A color steel plate, characterized in that, The high-performance coating is coated on the surface of a cleaned color steel plate.