CN112226141A - Composite coating and preparation method thereof - Google Patents

Composite coating and preparation method thereof Download PDF

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Publication number
CN112226141A
CN112226141A CN202011032938.3A CN202011032938A CN112226141A CN 112226141 A CN112226141 A CN 112226141A CN 202011032938 A CN202011032938 A CN 202011032938A CN 112226141 A CN112226141 A CN 112226141A
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boron nitride
silicon carbide
organic solvent
weight ratio
composite coating
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CN112226141B (en
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赵镍
张治财
齐福刚
欧阳晓平
易俊松
彭晓淳
张彪
余昊
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Hunan Bondzer Technology Co ltd
Xiangtan University
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Hunan Bondzer Technology Co ltd
Xiangtan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Abstract

The invention relates to the technical field of anticorrosive coatings, and discloses a composite coating and a preparation method thereof, wherein the composite coating comprises the following raw material components in parts by weight: based on 100 parts by weight of epoxy resin, the content of the hydrophobic silicon carbide/boron nitride compound is 0.5-50 parts by weight, the content of the auxiliary agent is 2-30 parts by weight, and the content of the organic solvent I is 50-180 parts by weight. The composite coating has good corrosion resistance and antifouling property, and has good wear resistance and impact resistance.

Description

Composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a composite coating and a preparation method thereof.
Background
The epoxy resin (EP) has the characteristics of strong corrosion resistance, good electrical insulation, high strength and the like, and also has good manufacturability such as strong adhesive force, normal-temperature operation, simple and convenient construction and the like, and the price of the epoxy resin is low, so that the epoxy resin is widely applied in various fields. The epoxy resin mainly plays a role of physical shielding in corrosion prevention, so that corrosion factors cannot reach the base material.
Epoxy resins are widely used in the field of coatings, but have some disadvantages, so that further improvement of the properties of epoxy resin coatings is limited. Such as: the epoxy resin molecule contains more than two epoxy groups, can be crosslinked and cured under the action of a curing agent to generate a network structure, and the property of the internal structure of the epoxy resin causes the epoxy resin to show relative brittleness in a macroscopic view; moreover, at the beginning of curing, the solvent dissolved in the resin is released continuously, which generates a very large number of micropores in the coating, the existence of which provides a path for the corrosive medium to reach the substrate, and the existence of which has a fatal influence on the overall corrosion resistance and hardness. Researchers at home and abroad usually adopt additives to modify the comprehensive properties of epoxy resin, such as synthetic rubber, nano materials and the like. However, the addition of synthetic rubbers, thermoplastic polymers, often results in a reduction in the performance of the epoxy coating in other respects.
As a mature product, the epoxy zinc-rich paint has positive correlation between the anticorrosion effect and the service life and the content of zinc powder in the paint, and generally the better effect can be achieved only when the content of the zinc powder is about 60 percent. Since zinc powder is consumed all the time in the service process, researchers are seeking modification methods orThe filler with more excellent other properties is selected. On the nano-material side SiO2、Ti、Al2O3Carbon nanotubes, graphene oxide, etc. have been widely used to improve the wear and corrosion resistance of EP. Due to the special structure of the graphene material, the graphene material has wide application in many fields, and many researchers fill graphene and graphene oxide as inorganic fillers into the coating, and all achieve good performance improvement, but due to the high price of the graphene material, the further development of the graphene material in the coating field is limited
SiC has the characteristics of corrosion resistance, high temperature resistance, high strength, good heat conductivity, impact resistance and the like, and the hardness of the silicon carbide is far higher than that of the common SiO2. SiC materials are always applied to the field of ceramics, and the application of SiC to the field of coatings is rare. The nano silicon carbide particles are used as fillers and added into the epoxy resin, so that the mechanical property of the resin can be enhanced to a certain extent. However, when the nano particles are directly added into the resin, the nano particles are easy to agglomerate, and the silicon carbide has hydrophilicity and can accelerate the permeation of corrosive media to a certain extent.
At present, silicon carbide is commonly used for ceramic materials and is applied to organic coatings less, and some researches also aim to directly add the silicon carbide into epoxy resin as an additive, so that the problem of nanoparticle agglomeration cannot be effectively solved, and the advantages of silicon carbide nanoparticles cannot be fully exerted.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a composite coating and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a composite coating material, which comprises the following raw material components in parts by weight: based on 100 parts by weight of epoxy resin, the content of the hydrophobic silicon carbide/boron nitride compound is 0.5-50 parts by weight, the content of the auxiliary agent is 2-30 parts by weight, and the content of the organic solvent I is 50-180 parts by weight.
Preferably, the content of the hydrophobic silicon carbide/boron nitride compound is 2-25 parts by weight, the content of the auxiliary agent is 6-20 parts by weight, and the content of the organic solvent I is 60-140 parts by weight, based on 100 parts by weight of the epoxy resin.
Preferably, the preparation method of the hydrophobic silicon carbide/boron nitride composite comprises the following steps:
(1) dispersing hydroxylated boron nitride and a siloxane coupling agent I in an organic solvent II, heating I, separating I, washing I, and drying I to obtain coupling agent grafted boron nitride;
dispersing II hydrophobic silicon carbide and a siloxane coupling agent II in an organic solvent III, heating II, separating II, washing II, and drying II to obtain coupling agent grafted silicon carbide;
(2) and dispersing the coupling agent grafted silicon carbide and the coupling agent grafted boron nitride in an organic solvent IV, heating the solution III, separating the solution III, washing the solution III, and drying the solution III to obtain the hydrophobic silicon carbide/boron nitride compound.
Further preferably, in the step (1), the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent I is 1: 0.1-2.
Preferably, in the step (1), the weight ratio of the hydroxylated boron nitride to the organic solvent II is 1: 300-500.
Preferably, the preparation method of the hydroxylated boron nitride comprises the following steps: dispersing the boron nitride IV in a mixed acid solution to obtain a suspension, heating the IV, separating the IV, washing the IV, and drying the IV to obtain hydroxylated boron nitride;
the mixed acid solution is a mixed solution of a sulfuric acid aqueous solution and a nitric acid aqueous solution, the molar concentration of the sulfuric acid aqueous solution is 12-18.4mol/L, the molar concentration of the nitric acid aqueous solution is 10-14.5mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1: 2-4.
Further preferably, the boron nitride is hexagonal boron nitride.
Preferably, the weight ratio of the boron nitride to the mixed acid solution is 1: 200-300.
Preferably, the dispersion IV is an ultrasonic dispersion, and the condition of the dispersion IV at least satisfies: the power is 100-;
the heating IV at least satisfies the following conditions: the temperature is 60-100 ℃, and the time is 6-18 h;
the condition of the dry IV at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
Preferably, in the step (1), the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent II is 1: 0.1-2.
Preferably, in the step (1), the weight ratio of the hydrophobic silicon carbide to the organic solvent III is 1: 300-500.
Preferably, the preparation method of the hydrophobic silicon carbide comprises the following steps:
dispersing silicon carbide and a hydrophobic modifier in an organic solvent V to obtain a suspension, mixing the suspension with water, heating V, separating V, washing V, and drying V to obtain hydrophobic silicon carbide;
wherein the weight ratio of the hydrophobic modifier to the silicon carbide is 1: 0.1-10.
Preferably, the weight ratio of the hydrophobic modifier to the organic solvent V is 1: 100-500.
Preferably, the weight ratio of the suspension to the water is 100: 1-2.
Preferably, the hydrophobic modifier is selected from at least one of hexadecyl trimethoxy silane, hexadecyl triethoxy silane, octadecyl trimethoxy silane, octadecyl triethoxy silane, 1H,2H, 2H-perfluoro octyl triethoxy silane and 1H,1H,2H, 2H-perfluoro octyl trimethoxy silane.
Preferably, the organic solvent V is selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
Preferably, the dispersion V is an ultrasonic dispersion, and the condition of the dispersion V at least satisfies: the power is 100-;
the condition of heating V at least satisfies: the temperature is 50-100 ℃, and the time is 2-6 h;
the condition of the drying V at least satisfies: the temperature is 60-100 ℃, and the time is 8-16 h.
Preferably, in step (1), the heating I is performed under at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of the drying I at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
Preferably, in step (1), the heating II is performed under at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of drying II at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
Preferably, said siloxane coupling agent I and said siloxane coupling agent II are each independently selected from at least one of KH540, KH-550, KH-560 and KH-570.
Preferably, in the step (2), the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is 1: 0.1-10.
Further preferably, the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is 1: 0.5-5.
Preferably, the method of dispersing III comprises: and ultrasonically dispersing the coupling agent grafted silicon carbide and the coupling grafted boron nitride in the same organic solvent respectively, wherein the power of ultrasonic dispersion is 100-200W, and the time of ultrasonic dispersion is 40-90min each time.
Further preferably, the weight ratio of the coupled grafted silicon carbide to the organic solvent IV is 1: 100-500.
Preferably, the condition for heating III at least satisfies: the temperature is 50-90 ℃ and the time is 2-6 h; the condition of drying III at least satisfies: the temperature is 50-70 ℃ and the time is 6-24 h.
Preferably, the organic solvent II, the organic solvent III and the organic solvent IV are each independently selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
More preferably, the epoxy resin is selected from at least one of CYD-011, CYD-014, E44, E20 and ES-020.
Preferably, the organic solvent I is selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
Preferably, the auxiliary agent is selected from at least one of a defoaming agent, a dispersing agent and an accelerator.
Preferably, the defoaming agent is selected from at least one of polyether modified silicone defoaming agent, isocyanate modified silicone defoaming agent, higher alcohol fatty acid ester defoaming agent and fatty amide defoaming agent;
the dispersing agent is selected from at least one of polyacrylate, butyl ester, N-methyl pyrrolidone, dimethyl formamide and stearic acid monoglyceride;
the accelerator is a fatty amine accelerator and/or an acid anhydride accelerator.
Further preferably, the polyether modified silicone defoamer is JQ-904; the isocyanate modified organic silicon defoamer is KH-597; the high-carbon alcohol fatty acid ester defoaming agent is SXP-110; the fatty amide antifoaming agent is DU-1262.
Further preferably, the aliphatic amine accelerator is at least one selected from the group consisting of 2,4, 6-tris (dimethylaminomethyl) phenol, EP-184 and triethanolamine, and the acid anhydride accelerator is N, N-dimethylbenzylamine and/or 1, 8-diazabicyclo-bicyclo (5,4,0) -7-undecene.
Typically, the auxiliaries are defoamers, dispersants and accelerators; the weight ratio of the defoaming agent to the dispersing agent to the accelerating agent is 1:0.5-2: 2-5.
In a second aspect, the present invention provides a method for preparing a composite coating, comprising the following steps:
s1, uniformly mixing the hydrophobic siloxane/boron nitride compound, the epoxy resin, the auxiliary agent and the organic solvent I to obtain a mixture;
s2, ball-milling the mixture obtained in the step (1) to obtain the composite coating;
wherein, 100 parts by weight of epoxy resin is taken as a reference, the addition amount of the hydrophobic silicon carbide/boron nitride compound is 0.5-50 parts by weight, the addition amount of the auxiliary agent is 2-30 parts by weight, and the addition amount of the organic solvent I is 50-180 parts by weight.
Preferably, the addition amount of the hydrophobic silicon carbide/boron nitride compound is 2-25 parts by weight, the addition amount of the auxiliary agent is 6-20 parts by weight, and the addition amount of the organic solvent I is 60-140 parts by weight, based on 100 parts by weight of the epoxy resin.
Preferably, the preparation method of the hydrophobic silicon carbide/boron nitride composite comprises the following steps:
(1) dispersing hydroxylated boron nitride and a siloxane coupling agent I in an organic solvent II, heating I, separating I, washing I, and drying I to obtain coupling agent grafted boron nitride;
dispersing II hydrophobic silicon carbide and a siloxane coupling agent II in an organic solvent III, heating II, separating II, washing II, and drying II to obtain coupling agent grafted silicon carbide;
(2) and dispersing the coupling agent grafted silicon carbide and the coupling agent grafted boron nitride in an organic solvent IV, heating the solution III, separating the solution III, washing the solution III, and drying the solution III to obtain the hydrophobic silicon carbide/boron nitride compound.
Further preferably, in the step (1), the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent I is 1: 0.1-2.
Preferably, in the step (1), the weight ratio of the hydroxylated boron nitride to the organic solvent II is 1: 300-500.
Preferably, the preparation method of the hydroxylated boron nitride comprises the following steps:
dispersing the boron nitride IV in a mixed acid solution to obtain a suspension, heating the IV, separating the IV, washing the IV, and drying the IV to obtain hydroxylated boron nitride;
the mixed acid solution is a mixed solution of a sulfuric acid aqueous solution and a nitric acid aqueous solution, the molar concentration of the sulfuric acid aqueous solution is 12-18.4mol/L, the molar concentration of the nitric acid aqueous solution is 10-14.5mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1: 2-4.
Further preferably, the boron nitride is hexagonal boron nitride.
Preferably, the weight ratio of the boron nitride to the mixed acid solution is 1: 200-300.
Preferably, the dispersion IV is an ultrasonic dispersion, and the condition of the dispersion IV at least satisfies: the power is 100-;
the heating IV at least satisfies the following conditions: the temperature is 60-100 ℃, and the time is 6-18 h;
the condition of the dry IV at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
Preferably, in the step (1), the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent II is 1: 0.1-2.
Preferably, in the step (1), the weight ratio of the hydrophobic silicon carbide to the organic solvent III is 1: 300-500;
preferably, the preparation method of the hydrophobic silicon carbide comprises the following steps:
dispersing silicon carbide and a hydrophobic modifier in an organic solvent V to obtain a suspension, mixing the suspension with water, heating V, separating V, washing V, and drying V to obtain hydrophobic silicon carbide;
wherein the weight ratio of the hydrophobic modifier to the silicon carbide is 1: 0.1-10.
Preferably, the weight ratio of the hydrophobic modifier to the organic solvent V is 1: 100-500.
Preferably, the weight ratio of the suspension to the water is 100: 1-2.
Preferably, the hydrophobic modifier is selected from at least one of hexadecyl trimethoxy silane, hexadecyl triethoxy silane, octadecyl trimethoxy silane, octadecyl triethoxy silane, 1H,2H, 2H-perfluoro octyl triethoxy silane and 1H,1H,2H, 2H-perfluoro octyl trimethoxy silane.
Preferably, the organic solvent V is selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
Preferably, the dispersion V is an ultrasonic dispersion, and the condition of the dispersion V at least satisfies: the power is 100-;
the condition of heating V at least satisfies: the temperature is 50-100 ℃, and the time is 2-6 h;
the condition of the drying V at least satisfies: the temperature is 60-100 ℃, and the time is 8-16 h.
Preferably, in step (1), the heating I is performed under at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of the drying I at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
Preferably, in step (1), the heating II is performed under at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of drying II at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
Preferably, said siloxane coupling agent I and said siloxane coupling agent II are each independently selected from at least one of KH540, KH-550, KH-560 and KH-570.
Preferably, in the step (2), the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is 1: 0.1-10.
Further preferably, the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is 1: 0.5-5.
Preferably, the method of dispersing III comprises: and ultrasonically dispersing the coupling agent grafted silicon carbide and the coupling grafted boron nitride in the same organic solvent respectively, wherein the power of ultrasonic dispersion is 100-200W, and the time of ultrasonic dispersion is 40-90min each time.
Further preferably, the weight ratio of the coupled grafted silicon carbide to the organic solvent IV is 1: 100-500.
Preferably, the condition for heating III at least satisfies: the temperature is 50-90 ℃ and the time is 2-6 h; the condition of drying III at least satisfies: the temperature is 50-70 ℃ and the time is 6-24 h.
Preferably, the organic solvent II, the organic solvent III and the organic solvent IV are each independently selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
More preferably, the epoxy resin is selected from at least one of CYD-011, CYD-014, E44, E20 and ES-020.
Preferably, the organic solvent I is selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
Preferably, the auxiliary agent is selected from at least one of a defoaming agent, a dispersing agent and an accelerator.
Preferably, the defoaming agent is selected from at least one of polyether modified silicone defoaming agent, isocyanate modified silicone defoaming agent, higher alcohol fatty acid ester defoaming agent and fatty amide defoaming agent;
the dispersing agent is selected from at least one of polyacrylate, butyl ester, N-methyl pyrrolidone, dimethyl formamide and stearic acid monoglyceride;
the accelerator is a fatty amine accelerator and/or an acid anhydride accelerator.
Further preferably, the polyether modified silicone defoamer is JQ-904; the isocyanate modified organic silicon defoamer is KH-597; the high-carbon alcohol fatty acid ester defoaming agent is SXP-110; the fatty amide antifoaming agent is DU-1262.
Further preferably, the aliphatic amine accelerator is at least one selected from the group consisting of 2,4, 6-tris (dimethylaminomethyl) phenol, EP-184 and triethanolamine, and the acid anhydride accelerator is N, N-dimethylbenzylamine and/or 1, 8-diazabicyclo-bicyclo (5,4,0) -7-undecene.
Typically, the auxiliaries are defoamers, dispersants and accelerators; the weight ratio of the defoaming agent to the dispersing agent to the accelerating agent is 1:0.5-2: 2-5.
Preferably: in step S2, the ball milling conditions at least satisfy: the rotation speed is 500-2000rpm, the temperature is 40-100 ℃, and the time is 4-24 h.
According to the composite coating provided by the invention, the hydrophobic siloxane/boron nitride compound is added into the coating of the epoxy resin, so that the hydrophobic siloxane/boron nitride compound is uniformly dispersed in the epoxy resin through the interaction of the hydrophobic siloxane/boron nitride compound, the epoxy resin, the assistant and the organic solvent I, and the corrosion resistance, the antifouling property, the impact resistance and the wear resistance of the composite coating can be effectively improved.
Drawings
FIG. 1 is a graph of water contact angle measurements for the composite coatings provided in example 2;
fig. 2 is an SEM image of the composite coating provided in example 3 coated on a substrate.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As mentioned above, the first aspect of the present invention provides a composite coating material, which comprises the following raw material components in parts by weight: based on 100 parts by weight of epoxy resin, the content of the hydrophobic silicon carbide/boron nitride compound is 0.5-50 parts by weight, the content of the auxiliary agent is 2-30 parts by weight, and the content of the organic solvent I is 50-180 parts by weight.
The hydrophobic silicon carbide is hydrophobically modified silicon carbide.
The inventor of the invention finds that the hydrophobic siloxane/boron nitride compound is added into the epoxy resin coating, so that the hydrophobic siloxane/boron nitride compound can be uniformly dispersed in the epoxy resin through the interaction of the hydrophobic siloxane/boron nitride compound, the epoxy resin, the auxiliary agent and the organic solvent I, and the corrosion resistance, the antifouling property, the impact resistance and the wear resistance of the composite coating can be effectively improved.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the content of the hydrophobic silicon carbide/boron nitride composite is preferably 2 to 25 parts by weight, the content of the auxiliary agent is preferably 6 to 20 parts by weight, and the content of the organic solvent I is preferably 60 to 140 parts by weight, based on 100 parts by weight of the epoxy resin.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the preparation method of the hydrophobic silicon carbide/boron nitride composite comprises the following steps:
(1) dispersing hydroxylated boron nitride and a siloxane coupling agent I in an organic solvent II, heating I, separating I, washing I, and drying I to obtain coupling agent grafted boron nitride;
dispersing II hydrophobic silicon carbide and a siloxane coupling agent II in an organic solvent III, heating II, separating II, washing II, and drying II to obtain coupling agent grafted silicon carbide;
(2) and dispersing the coupling agent grafted silicon carbide and the coupling agent grafted boron nitride in an organic solvent IV, heating the solution III, separating the solution III, washing the solution III, and drying the solution III to obtain the hydrophobic silicon carbide/boron nitride compound.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite material, the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent I in the step (1) is preferably 1: 0.1-2.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the hydroxylated boron nitride to the organic solvent II in the step (1) is preferably 1: 300-500.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the preparation method of the hydroxylated boron nitride comprises the following steps: dispersing the boron nitride IV in a mixed acid solution to obtain a suspension, heating the IV, separating the IV, washing the IV, and drying the IV to obtain hydroxylated boron nitride;
the mixed acid solution is a mixed solution of a sulfuric acid aqueous solution and a nitric acid aqueous solution, the molar concentration of the sulfuric acid aqueous solution is 12-18.4mol/L, the molar concentration of the nitric acid aqueous solution is 10-14.5mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1: 2-4.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the boron nitride is preferably hexagonal boron nitride.
In order to further improve the corrosion resistance, the antifouling property and the wear resistance of the composite coating, the weight ratio of the boron nitride to the mixed acid solution is preferably 1: 200-300.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the dispersion IV is an ultrasonic dispersion, and the condition of the dispersion IV at least satisfies: the power is 100-; the heating IV at least satisfies the following conditions: the temperature is 60-100 ℃, and the time is 6-18 h; the condition of the dry IV at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent II in the step (1) is preferably 1: 0.1-2.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the hydrophobic silicon carbide to the organic solvent III in the step (1) is preferably 1: 300-500.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the preparation method of the hydrophobic silicon carbide comprises the following steps: dispersing silicon carbide and a hydrophobic modifier in an organic solvent V to obtain a suspension, mixing the suspension with water, heating V, separating V, washing V, and drying V to obtain hydrophobic silicon carbide;
wherein the weight ratio of the hydrophobic modifier to the silicon carbide is 1: 0.1-10.
In order to further improve the corrosion resistance and the antifouling property of the composite coating, the weight ratio of the hydrophobic modifier to the silicon carbide is preferably 1: 0.5-5.
In order to further improve the corrosion resistance and the antifouling property of the composite coating, the weight ratio of the hydrophobic modifier to the organic solvent V is preferably 1: 100-500.
In order to further improve the corrosion resistance and the antifouling performance of the composite coating, the weight ratio of the suspension to the water is preferably 100: 1-2.
In order to further improve the corrosion resistance and antifouling performance of the composite coating, the hydrophobic modifier is preferably selected from at least one of hexadecyl trimethoxy silane, hexadecyl triethoxy silane, octadecyl trimethoxy silane, octadecyl triethoxy silane, 1H, 2H-perfluoro octyl triethoxy silane and 1H, 2H-perfluoro octyl trimethoxy silane.
In order to further improve the corrosion prevention and antifouling performance of the composite coating material, the organic solvent V is preferably at least one selected from the group consisting of absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
In order to further improve the corrosion resistance and the antifouling performance of the composite coating, preferably, the dispersion V is an ultrasonic dispersion, and the condition of the dispersion V at least satisfies: the power is 100-; the condition of heating V at least satisfies: the temperature is 50-100 ℃, and the time is 2-6 h; the condition of the drying V at least satisfies: the temperature is 60-100 ℃, and the time is 8-16 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, it is preferable that in the step (1), the heating I satisfies at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of the drying I at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, in step (1), the heating II preferably satisfies at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of drying II at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
In order to further improve the corrosion prevention property, antifouling property, impact resistance property and abrasion resistance property of the composite coating material, preferably, the siloxane coupling agent I and the siloxane coupling agent II are independently selected from at least one of KH540, KH-550, KH-560 and KH-570.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, in step (2), the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is preferably 1: 0.1-10.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is preferably 1: 0.5-5.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating, preferably, the method of dispersing III comprises: and ultrasonically dispersing the coupling agent grafted silicon carbide and the coupling grafted boron nitride in the same organic solvent respectively, wherein the power of ultrasonic dispersion is 100-200W, and the time of ultrasonic dispersion is 40-90min each time.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the coupled grafted silicon carbide to the organic solvent IV is preferably 1: 100-500.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, it is preferable that the condition of heating III at least satisfies: the temperature is 50-90 ℃ and the time is 2-6 h; the condition of drying III at least satisfies: the temperature is 50-70 ℃ and the time is 6-24 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating material, it is preferable that the organic solvent II, the organic solvent III and the organic solvent IV are each independently selected from at least one of absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the epoxy resin is preferably selected from at least one of CYD-011, CYD-014, E44, E20 and ES-020.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating material, the organic solvent I is preferably selected from at least one of absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating material, it is preferable that the auxiliary agent is at least one selected from the group consisting of a defoaming agent, a dispersing agent and an accelerator.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the defoaming agent is preferably selected from at least one of polyether modified organic silicon defoaming agent, isocyanate modified organic silicon defoaming agent, higher alcohol fatty acid ester defoaming agent and fatty amide defoaming agent;
the dispersing agent is selected from at least one of polyacrylate, butyl ester, N-methyl pyrrolidone, dimethyl formamide and stearic acid monoglyceride;
the accelerator is a fatty amine accelerator and/or an acid anhydride accelerator.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the polyether modified organic silicon defoamer is JQ-904; the isocyanate modified organic silicon defoamer is KH-597; the high-carbon alcohol fatty acid ester defoaming agent is SXP-110; the fatty amide antifoaming agent is DU-1262.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating, the aliphatic amine accelerator is preferably at least one selected from 2,4, 6-tris (dimethylaminomethyl) phenol, EP-184 and triethanolamine, and the acid anhydride accelerator is N, N-dimethylbenzylamine and/or 1, 8-diazabicyclo-bicyclo (5,4,0) -7-undecene.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the auxiliary agent is preferably a defoaming agent, a dispersing agent and an accelerating agent; the weight ratio of the defoaming agent to the dispersing agent to the accelerating agent is 1:0.5-2: 2-5.
As described above, the second aspect of the present invention provides a method for preparing a composite coating material, comprising the steps of:
s1, uniformly mixing the hydrophobic siloxane/boron nitride compound, the epoxy resin, the auxiliary agent and the organic solvent I to obtain a mixture;
s2, ball-milling the mixture obtained in the step (1) to obtain the composite coating;
wherein, 100 parts by weight of epoxy resin is taken as a reference, the addition amount of the hydrophobic silicon carbide/boron nitride compound is 0.5-50 parts by weight, the addition amount of the auxiliary agent is 2-30 parts by weight, and the addition amount of the organic solvent I is 50-180 parts by weight.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the addition amount of the hydrophobic silicon carbide/boron nitride composite is preferably 2 to 25 parts by weight, the addition amount of the auxiliary agent is preferably 6 to 20 parts by weight, and the addition amount of the organic solvent I is preferably 60 to 140 parts by weight, based on 100 parts by weight of the epoxy resin.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the preparation method of the hydrophobic silicon carbide/boron nitride composite comprises the following steps:
(1) dispersing hydroxylated boron nitride and a siloxane coupling agent I in an organic solvent II, heating I, separating I, washing I, and drying I to obtain coupling agent grafted boron nitride;
dispersing II hydrophobic silicon carbide and a siloxane coupling agent II in an organic solvent III, heating II, separating II, washing II, and drying II to obtain coupling agent grafted silicon carbide;
(2) and dispersing the coupling agent grafted silicon carbide and the coupling agent grafted boron nitride in an organic solvent IV, heating the solution III, separating the solution III, washing the solution III, and drying the solution III to obtain the hydrophobic silicon carbide/boron nitride compound.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite material, the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent I in the step (1) is preferably 1: 0.1-2.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the hydroxylated boron nitride to the organic solvent II in the step (1) is preferably 1: 300-500.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the preparation method of the hydroxylated boron nitride comprises the following steps: dispersing the boron nitride IV in a mixed acid solution to obtain a suspension, heating the IV, separating the IV, washing the IV, and drying the IV to obtain hydroxylated boron nitride;
the mixed acid solution is a mixed solution of a sulfuric acid aqueous solution and a nitric acid aqueous solution, the molar concentration of the sulfuric acid aqueous solution is 12-18.4mol/L, the molar concentration of the nitric acid aqueous solution is 10-14.5mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1: 2-4.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the boron nitride is preferably hexagonal boron nitride.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the boron nitride to the mixed acid solution is preferably 1: 200-300.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the dispersion IV is an ultrasonic dispersion, and the condition of the dispersion IV at least satisfies: the power is 100-; the heating IV at least satisfies the following conditions: the temperature is 60-100 ℃, and the time is 6-18 h; the condition of the dry IV at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent II in the step (1) is preferably 1: 0.1-2.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, in the step (1), the weight ratio of the hydrophobic silicon carbide to the organic solvent III is 1: 300-500;
in order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, the preparation method of the hydrophobic silicon carbide comprises the following steps: dispersing silicon carbide and a hydrophobic modifier in an organic solvent V to obtain a suspension, mixing the suspension with water, heating V, separating V, washing V, and drying V to obtain hydrophobic silicon carbide;
wherein the weight ratio of the hydrophobic modifier to the silicon carbide is 1: 0.1-10.
In order to further improve the corrosion resistance and the antifouling property of the composite coating, the weight ratio of the hydrophobic modifier to the silicon carbide is preferably 1: 0.5-5.
In order to further improve the corrosion resistance and the antifouling property of the composite coating, the weight ratio of the hydrophobic modifier to the organic solvent V is preferably 1: 100-500.
In order to further improve the corrosion resistance and the antifouling performance of the composite coating, the weight ratio of the suspension to the water is preferably 100: 1-2.
In order to further improve the corrosion resistance and antifouling performance of the composite coating, the hydrophobic modifier is preferably selected from at least one of hexadecyl trimethoxy silane, hexadecyl triethoxy silane, octadecyl trimethoxy silane, octadecyl triethoxy silane, 1H, 2H-perfluoro octyl triethoxy silane and 1H, 2H-perfluoro octyl trimethoxy silane.
In order to further improve the corrosion prevention and antifouling performance of the composite coating material, the organic solvent V is preferably at least one selected from the group consisting of absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
In order to further improve the corrosion resistance and the antifouling performance of the composite coating, preferably, the dispersion V is an ultrasonic dispersion, and the condition of the dispersion V at least satisfies: the power is 100-; the condition of heating V at least satisfies: the temperature is 50-100 ℃, and the time is 2-6 h; the condition of the drying V at least satisfies: the temperature is 60-100 ℃, and the time is 8-16 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, it is preferable that in the step (1), the heating I satisfies at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of the drying I at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, in step (1), the heating II preferably satisfies at least the following conditions: the temperature is 60-80 ℃, and the time is 2-6 h; the condition of drying II at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
In order to further improve the corrosion prevention property, antifouling property, impact resistance property and abrasion resistance property of the composite coating material, preferably, the siloxane coupling agent I and the siloxane coupling agent II are independently selected from at least one of KH540, KH-550, KH-560 and KH-570.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, in step (2), the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is preferably 1: 0.1-10.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is preferably 1: 0.5-5.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating, preferably, the method of dispersing III comprises: and ultrasonically dispersing the coupling agent grafted silicon carbide and the coupling grafted boron nitride in the same organic solvent respectively, wherein the power of ultrasonic dispersion is 100-200W, and the time of ultrasonic dispersion is 40-90min each time.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the weight ratio of the coupled grafted silicon carbide to the organic solvent IV is preferably 1: 100-500.
In order to further improve the corrosion resistance, the antifouling property and the wear resistance of the composite coating, it is preferable that the condition of the heating III at least satisfies: the temperature is 50-90 ℃ and the time is 2-6 h; the condition of drying III at least satisfies: the temperature is 50-70 ℃ and the time is 6-24 h.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating material, it is preferable that the organic solvent II, the organic solvent III and the organic solvent IV are each independently selected from at least one of absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the epoxy resin is preferably selected from at least one of CYD-011, CYD-014, E44, E20 and ES-020.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating material, the organic solvent I is preferably selected from at least one of absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating material, it is preferable that the auxiliary agent is at least one selected from the group consisting of a defoaming agent, a dispersing agent and an accelerator.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the defoamer is preferably selected from at least one of polyether modified silicone defoamer, isocyanate modified silicone defoamer, higher alcohol fatty acid ester defoamer and fatty amide defoamer;
the dispersing agent is selected from at least one of polyacrylate, butyl ester, N-methyl pyrrolidone, dimethylformamide and stearic acid monoglyceride;
the accelerator is a fatty amine accelerator and/or an acid anhydride accelerator.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the polyether modified organic silicon defoamer is JQ-904; the isocyanate modified organic silicon defoamer is KH-597; the high-carbon alcohol fatty acid ester defoaming agent is SXP-110; the fatty amide antifoaming agent is DU-1262.
In order to further improve the corrosion resistance, antifouling property, impact resistance and abrasion resistance of the composite coating, the aliphatic amine accelerator is preferably at least one selected from 2,4, 6-tris (dimethylaminomethyl) phenol, EP-184 and triethanolamine, and the acid anhydride accelerator is N, N-dimethylbenzylamine and/or 1, 8-diazabicyclo-bicyclo (5,4,0) -7-undecene.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, the auxiliary agent is preferably a defoaming agent, a dispersing agent and an accelerating agent; the weight ratio of the defoaming agent to the dispersing agent to the accelerating agent is 1:0.5-2: 2-5.
In order to further improve the corrosion resistance, antifouling property, impact resistance and wear resistance of the composite coating, preferably, in step S2, the ball milling conditions at least include: the rotation speed is 500-2000rpm, the temperature is 40-100 ℃, and the time is 4-24 h. Preferably, the weight ratio of the materials to the balls is 1: 1-10; more preferably, the weight ratio of material to ball is 1: 1-5. The weight ratio of material to balls used in the following examples was 1: 2.
In the present invention, the solvent used for the washing may be water, ethanol, acetone, or the like.
The present invention will be described in detail below by way of examples.
In the invention, the abrasion loss is measured according to the GB/T1768-2006 detection standard; the impact resistance is measured according to GB 1732-79 (88) paint film impact resistance measuring method; the acid and alkali corrosion resistance is measured according to a chemical reagent resistance measuring method of a paint film of GB 1763-1979; the neutral salt corrosion resistance is measured according to the determination of the neutral salt fog resistance of GB-T1771-2007 colored paint and varnish; the contact angle adopts a shape image analysis method, water drops are dripped on the surface of a sample, a shape image of the water drops is obtained through a microscope and a camera, and then the contact angle of the water drops in the image is calculated by digital image processing and calculation.
Wherein the paint film abrasion instrument is manufactured by a Dageda precision instrument, Inc., and has the model number of BGD-523; the contact angle measuring instrument is purchased from Baiohlin science and technology Limited and has the model number of DSA 100; the paint film impactor is purchased from Dageda precision instruments, Inc., and has the model number BGD-304; the field emission scanning electron microscope is purchased from Carl Caisis, Inc. and is of the MERLIN Compact type; the composite salt spray test box is purchased from Dageda precision instruments Co., Ltd, and has the model number of BGD-887.
Organic solvent: anhydrous ethanol (hereinafter referred to as organic solvent-1), glycerol (hereinafter referred to as organic solvent-2), ethylene glycol ether (hereinafter referred to as organic solvent-3), styrene (hereinafter referred to as organic solvent-4) and triethanolamine (hereinafter referred to as organic solvent-5) are all commercially available from the national institutes of medicine.
Hydrophobic modifier: hexadecyl trimethoxysilane (hereinafter referred to as hydrophobic modifier-1) was purchased from Allantin holdings group Co., Ltd, and octadecyl triethoxysilane (hereinafter referred to as hydrophobic modifier-2) was purchased from Nanjing Sisco organosilicon Co., Ltd under the number H106567; 1H,1H,2H, 2H-perfluorooctyltriethoxysilane (hereinafter referred to as hydrophobic modifier-3) was purchased from Allantin Secretaria group Co., Ltd, and assigned number T162293; octadecyltrimethoxysilane (hereinafter referred to as hydrophobic modifier-3) was purchased from Nanjing Siscob Silicone Co., Ltd.
Siloxane coupling agent: KH540 (hereinafter referred to as siloxane coupling agent-1) was purchased from Allantin Seikagaku Co., Ltd., No. A100943-; KH-550 (hereinafter referred to as siloxane coupling agent-2) was purchased from Allantin controlled-Strand group, Inc.; KH-560 (hereinafter referred to as siloxane coupling agent-3) available from Arlatin, Consumer group, Inc. under the number G107576; KH-570 (hereinafter referred to as siloxane coupling agent-4) was purchased from Allantin controlled-stock group, Inc.
Epoxy resin: CYD-011 (hereinafter referred to as epoxy resin-1) purchased from Baling chemical Co., Ltd, epoxy equivalent g/eq (450-; e44 (hereinafter referred to as epoxy resin-3) was purchased from Baling chemical Co., Ltd, and had an epoxy equivalent g/eq (410- & ltSUB & gt 470), a hydrolyzable chlorine content (mass fraction) & lt, 0.10, a softening point (. degree. C.) of 12-20, a dissolution viscosity (25 ℃ C.) of L-Q, a volatile content (mass fraction) & lt, 1, and a chroma (Gardner number) & lt, 1; e20 (hereinafter referred to as epoxy resin-4) by Balin chemical Co., Ltd., epoxy equivalent g/eq (580-610), hydrolyzable chlorine (mass fraction) of 0.10 or less, softening point (. degree. C.) of 80 to 85, dissolution viscosity (25 ℃ C.) I-L, volatile matter (mass fraction) of 0.60 or less, chroma (Gardner number) of 0.5 or less; ES-020 (hereinafter referred to as epoxy-5) by Baling chemical Co., Ltd., molecular weight: 16000, intrinsic viscosity: 0.50, glass transition temperature: 47, softening point: 120, acid value: 3, hydroxyl value: 4-8, tensile strength 47.
Auxiliary agent: JQ-904 (belonging to polyether modified organic silicon defoamer, hereinafter referred to as adjuvant-1) was purchased from Jingqi chemical technology Co., Ltd, Fushan; KH-597 (belonging to isocyanate modified silicone defoamer, hereinafter referred to as adjuvant-2) was purchased from JSCICA CHEMICAL CO., Hangzhou; DU-1262 (belonging to the class of fatty amide antifoaming agents, hereinafter referred to as adjuvant-3) was purchased from New materials research institute, Inc. in Dongguan City; polyacrylate (hereinafter referred to as an auxiliary agent-4) was purchased from Antai Fine chemical Co., Ltd, Dongguan, and numbered G-30; n-methylpyrrolidone (hereinafter referred to as adjuvant-5) was purchased from Allantin holdings group, Inc. under the number M120510; dimethylformamide (hereinafter referred to as adjuvant-6) was purchased from Allantin, Consumer group, Inc., and assigned number D119450; 2,4, 6-tris (dimethylaminomethyl) phenol (hereinafter referred to as adjuvant-7) was purchased from Chuzhou Heishan electronic materials Co., Ltd., under the number DMP-30; 1, 8-diazabicyclo-bicyclo (5,4,0) -7-undecene (hereinafter referred to as adjuvant-8) is available from Shanghai, bright-day Innovative materials, Inc. under the number PFWT-153; n, N-dimethylbenzylamine (hereinafter referred to as adjuvant-9) was purchased from Arlatin GmbH, and assigned the number D110950.
Hexagonal boron nitride available from Shanghai Michelin Biochemical technology, Inc. under the number B874955; cubic boron nitride available from alatin holdings group ltd under the designation B106032; silicon carbide was purchased from alatin holdings group ltd and numbered S104653; other drugs are purchased from the national drug group.
Preparation of hydrophobic silicon carbide/boron nitride composite:
preparation example 1
(1) Ultrasonically dispersing hexagonal boron nitride (the ultrasonic power is 160W, the ultrasonic time is 45min) in a mixed acid solution-1 (the molar solubility of a sulfuric acid aqueous solution is 16mol/L, the solubility of a nitric acid aqueous solution is 12mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1:3) to obtain a suspension, wherein the weight ratio of the boron nitride to the mixed acid solution is 1:250, heating (the temperature is 80 ℃ and the time is 12h), filtering, separating, washing for multiple times, and drying (the temperature is 80 ℃ and the time is 16h) to obtain hydroxylated boron nitride;
ultrasonically dispersing silicon carbide and hydrophobic modifier-1 (the ultrasonic power is 160W, the ultrasonic time is 45min) in an organic solvent-1 to obtain a suspension, wherein the weight ratio of the hydrophobic modifier-1 to the silicon carbide to the organic solvent-1 is 1:3:300, and the weight ratio of the suspension to water is 1: 0.02 mixing, heating (the temperature is 75 ℃ and the time is 4 hours), filtering and separating, washing for many times, and drying (the temperature is 80 ℃ and the time is 12 hours) to obtain hydrophobic silicon carbide;
(2) dispersing hydroxylated boron nitride and siloxane coupling agent-1 in organic solvent-2, wherein the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent-1 to the organic solvent-2 is 1:1: 400; heating (the temperature is 80 ℃ and the time is 4 hours), filtering, separating, washing for many times, and drying (the temperature is 80 ℃ and the time is 16 hours) to obtain the coupling grafted boron nitride;
dispersing hydrophobic silicon carbide and siloxane coupling agent-1 in organic solvent-2, wherein the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent-1 to the organic solvent-2 is 1:1: 400; heating (the temperature is 70 ℃ and the time is 4 hours), filtering, separating, washing for multiple times, and drying (the temperature is 80 ℃ and the time is 16 hours) to obtain the coupling grafted silicon carbide;
(3) respectively ultrasonically dispersing the coupled grafted silicon carbide and the coupled grafted boron nitride (the ultrasonic power is 160W, the ultrasonic time is 60min each time) in the same organic solvent-2 to obtain a suspension, wherein the weight ratio of the hydrophobic coupled grafted silicon carbide to the coupled grafted boron nitride to the organic solvent-2 is 1:3:300, heating (the temperature is 70 ℃ and the time is 4h), filtering, separating, washing for multiple times, and drying (the temperature is 60 ℃ and the time is 16h) to obtain the hydrophobic silicon carbide/boron nitride compound (hereinafter referred to as compound-1).
Preparation example 2
(1) Ultrasonically dispersing hexagonal boron nitride (the ultrasonic power is 100W, the ultrasonic time is 30min) in a mixed acid solution-2 (the molar solubility of a sulfuric acid aqueous solution is 12mol/L, the solubility of a nitric acid aqueous solution is 14.5mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1:4) to obtain a suspension, wherein the weight ratio of the boron nitride to the mixed acid solution is 1:200, heating (the temperature is 60 ℃ and the time is 18h), filtering, separating, washing for multiple times, and drying (the temperature is 60 ℃ and the time is 24h) to obtain hydroxylated boron nitride;
ultrasonically dispersing silicon carbide and hydrophobic modifier-2 (the ultrasonic power is 100W, the ultrasonic time is 30min) in an organic solvent-2 to obtain a suspension, wherein the weight ratio of the hydrophobic modifier-2 to the silicon carbide to the organic solvent-2 is 1:0.5:100, and the weight ratio of the suspension to water is 1: 0.01, mixing, heating (50 ℃ for 6 hours), filtering, separating, washing for multiple times, and drying (60 ℃ for 16 hours) to obtain hydrophobic silicon carbide;
(2) dispersing hydroxylated boron nitride and siloxane coupling agent-2 in organic solvent-3, wherein the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent-2 to the organic solvent-3 is 1:0.1: 300; heating (the temperature is 60 ℃ and the time is 6 hours), filtering, separating, washing for many times, and drying (the temperature is 60 ℃ and the time is 24 hours) to obtain the coupling grafted boron nitride;
dispersing hydrophobic silicon carbide and siloxane coupling agent-2 in an organic solvent-3, wherein the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent-2 to the organic solvent-3 is 1:0.1: 300; heating (the temperature is 60 ℃ and the time is 6 hours), filtering, separating, washing for multiple times, and drying (the temperature is 60 ℃ and the time is 24 hours) to obtain the coupling grafted silicon carbide;
(3) respectively ultrasonically dispersing the coupled grafted silicon carbide and the coupled grafted boron nitride (the ultrasonic power is 100W, the ultrasonic time is 40min each time) in the same organic solvent-3 to obtain a suspension, wherein the weight ratio of the hydrophobic coupled grafted silicon carbide to the coupled grafted boron nitride to the organic solvent-3 is 1:0.5:100, heating (the temperature is 50 ℃ and the time is 6h), filtering, separating, washing for multiple times, and drying (the temperature is 50 ℃ and the time is 24h) to obtain a hydrophobic silicon carbide/boron nitride compound (hereinafter referred to as compound-2).
Preparation example 3
(1) Ultrasonically dispersing hexagonal boron nitride (the ultrasonic power is 200W, the ultrasonic time is 60min) in a mixed acid solution-3 (the molar solubility of a sulfuric acid aqueous solution is 18.4mol/L, the solubility of a nitric acid aqueous solution is 10mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1:2) to obtain a suspension, wherein the weight ratio of the boron nitride to the mixed acid solution is 1:300, heating (the temperature is 100 ℃ and the time is 6h), filtering, separating, washing for multiple times, and drying (the temperature is 100 ℃ and the time is 6h) to obtain hydroxylated boron nitride;
ultrasonically dispersing silicon carbide, a hydrophobic modifier-3 and a hydrophobic modifier-4 (the ultrasonic power is 200W, and the ultrasonic time is 60min) in an organic solvent-4 to obtain a suspension, wherein the weight ratio of the hydrophobic modifier-3 to the hydrophobic modifier-4 to the silicon carbide to the organic solvent-4 is 0.5:0.5:5:500, and the weight ratio of the suspension to water is 1: 0.02 mixing, heating (the temperature is 100 ℃ and the time is 2 hours), filtering and separating, washing for multiple times, and drying (the temperature is 100 ℃ and the time is 8 hours) to obtain hydrophobic silicon carbide;
(2) dispersing hydroxylated boron nitride, siloxane coupling agent-3 and siloxane coupling agent-4 in organic solvent-4, wherein the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent-3 to the siloxane coupling agent-4 to the organic solvent-4 is 1:1:1: 500; heating (the temperature is 80 ℃ and the time is 2 hours), filtering, separating, washing for multiple times, and drying (the temperature is 100 ℃ and the time is 6 hours) to obtain the coupling grafted boron nitride;
dispersing hydrophobic silicon carbide, a siloxane coupling agent-3 and a siloxane coupling agent-4 in an organic solvent-4, wherein the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent-3 to the siloxane coupling agent-4 to the organic solvent-4 is 1:0.5:1.5: 500; heating (the temperature is 80 ℃ and the time is 2 hours), filtering, separating, washing for multiple times, and drying (the temperature is 100 ℃ and the time is 6 hours) to obtain the coupling grafted silicon carbide;
(3) respectively ultrasonically dispersing the coupled grafted silicon carbide and the coupled grafted boron nitride (the ultrasonic power is 200W, the ultrasonic time is 90min each time) in the same organic solvent-5 to obtain a suspension, wherein the weight ratio of the hydrophobic coupled grafted silicon carbide to the coupled grafted boron nitride to the organic solvent-5 is 1:5:500, heating (the temperature is 90 ℃ and the time is 2h), filtering, separating, washing for multiple times, and drying (the temperature is 70 ℃ and the time is 6h) to obtain a hydrophobic silicon carbide/boron nitride compound (hereinafter referred to as compound-3).
Preparation example 4
The difference from preparation example 2 is that:
(1) in the step (1), the hydrophobic modifier is changed into hydrophobic modifier-4, and the weight ratio of the hydrophobic modifier-4, the silicon carbide and the organic solvent-2 is 1:0.1: 100;
(2) in the step (3), the weight ratio of the hydrophobic coupling grafted silicon carbide to the coupling grafted boron nitride to the organic solvent-3 is 1:0.1: 100;
the hydrophobic silicon carbide/boron nitride composite prepared in this preparation example is referred to as composite-4.
Preparation example 5
The difference from preparation example 3 is that:
(1) in the step (1), the hydrophobic modifier is changed into hydrophobic modifier-5, and the weight ratio of the hydrophobic modifier-5 to the silicon carbide to the organic solvent-4 is 1:10: 500;
(2) in the step (3), the weight ratio of the hydrophobic coupling grafted silicon carbide to the coupling grafted boron nitride to the organic solvent-3 is 1:10: 500;
the hydrophobic silicon carbide/boron nitride composite prepared in this preparation example is referred to as composite-5.
Preparation example 6
The difference from preparation example 2 is that: in the step (1), the hexagonal boron nitride is changed into the cubic boron nitride; the hydrophobic silicon carbide/boron nitride composite prepared in this preparation example is referred to as composite-6.
Preparation example 7
The difference from preparation example 2 is that: in the step (1), hexagonal boron nitride is ultrasonically dispersed (the ultrasonic power is 100W, the ultrasonic time is 45min) into a mixed alkali solution (a mixed solution of sodium hydroxide and potassium hydroxide, the solubility of hydroxyl ions is 5mol/L) to obtain a suspension, wherein the weight ratio of the boron nitride to the mixed alkali solution is 1:250, the boron nitride and the mixed alkali solution are heated (the temperature is 80 ℃ and the time is 12 hours), and then the boron nitride is filtered, separated, washed for multiple times and dried (the temperature is 80 ℃ and the time is 16 hours) to obtain hydroxylated boron nitride;
this preparation example prepared a hydrophobic silicon carbide/boron nitride composite called composite-7.
Unless otherwise specified, the following represents 50g per part by weight.
Example 1
S1, mixing 15 parts by weight of hydrophobic siloxane/boron nitride compound-1, 100 parts by weight of epoxy resin-1, 2.2 parts by weight of assistant-4, 7.6 parts by weight of assistant-7 and 100 parts by weight of organic solvent-1 uniformly to obtain a mixture;
s2, ball-milling the mixture obtained in the step (1) to obtain the composite coating;
wherein the ball milling speed is 1500rpm, the temperature is 70 ℃, and the time is 12 h.
Example 2
Examples 2 to 6 were carried out by the same procedure as in comparative example 1, except for the differences shown in tables 1 and 2, unless otherwise specified.
TABLE 1
Figure BDA0002704301330000211
TABLE 2
Figure BDA0002704301330000221
Comparative example 2
S1, uniformly mixing 4.8 parts by weight of siloxane, 0.4 part by weight of hydrophobic modifier-3, 0.4 part by weight of hydrophobic modifier-4, 11 parts by weight of hexagonal boron nitride, 14.8 parts by weight of siloxane coupling agent-3, 18.2 parts by weight of siloxane coupling agent-3, 100 parts by weight of epoxy resin-5, 3.8 parts by weight of assistant-2, 7.5 parts by weight of assistant-6, 18.7 parts by weight of assistant-8 and 180 parts by weight of organic solvent-1 to obtain a mixture;
s2, ball-milling the mixture obtained in the step (1) to obtain the composite coating;
wherein the ball milling speed is 2000rpm, the temperature is 40 ℃, and the time is 24 h.
Test example
The coatings obtained in the above examples and comparative examples were subjected to measurements of the physical and chemical parameters, which are given in Table 3.
TABLE 3
Figure BDA0002704301330000231
The coating was sprayed onto a substrate with a fracture surface configuration as shown in FIG. 2 and was measured for contact angle as shown in FIG. 1. The combination of the above data shows that when the hydrophobic siloxane/boron nitride compound is added into the epoxy resin coating, the hydrophobic siloxane/boron nitride compound can be uniformly dispersed in the epoxy resin through the interaction between the hydrophobic siloxane/boron nitride compound and the epoxy resin, the additive and the organic solvent I, so that the corrosion resistance, the impact resistance and the wear resistance of the composite coating can be effectively improved, and the antifouling property of the composite coating can be improved by improving the hydrophobic property of the composite coating.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. The composite coating is characterized by comprising the following raw material components in parts by weight: based on 100 parts by weight of epoxy resin, the content of the hydrophobic silicon carbide/boron nitride compound is 0.5-50 parts by weight, the content of the auxiliary agent is 2-30 parts by weight, and the content of the organic solvent I is 50-180 parts by weight.
2. The composite coating according to claim 1, wherein the hydrophobic silicon carbide/boron nitride composite is contained in an amount of 2 to 25 parts by weight, the auxiliary is contained in an amount of 6 to 20 parts by weight, and the organic solvent I is contained in an amount of 60 to 140 parts by weight, based on 100 parts by weight of the epoxy resin.
3. The composite coating of claim 1, wherein the hydrophobic silicon carbide/boron nitride composite is prepared by a method comprising:
(1) dispersing hydroxylated boron nitride and a siloxane coupling agent I in an organic solvent II, heating I, separating I, washing I, and drying I to obtain coupling agent grafted boron nitride;
dispersing II hydrophobic silicon carbide and a siloxane coupling agent II in an organic solvent III, heating II, separating II, washing II, and drying II to obtain coupling agent grafted silicon carbide;
(2) and dispersing the coupling agent grafted silicon carbide and the coupling agent grafted boron nitride in an organic solvent IV, heating the solution III, separating the solution III, washing the solution III, and drying the solution III to obtain the hydrophobic silicon carbide/boron nitride compound.
4. The composite coating material according to claim 3, wherein in the step (1), the weight ratio of the hydroxylated boron nitride to the siloxane coupling agent I is 1: 0.1-2;
preferably, the weight ratio of the hydroxylated boron nitride to the organic solvent II is 1: 300-500;
the preparation method of the hydroxylated boron nitride comprises the following steps:
dispersing the boron nitride IV in a mixed acid solution to obtain a suspension, heating the IV, separating the IV, washing the IV, and drying the IV to obtain hydroxylated boron nitride;
the mixed acid solution is a mixed solution of a sulfuric acid aqueous solution and a nitric acid aqueous solution, the molar concentration of the sulfuric acid aqueous solution is 12-18.4mol/L, the molar concentration of the nitric acid aqueous solution is 10-14.5mol/L, and the weight ratio of the sulfuric acid aqueous solution to the nitric acid aqueous solution is 1: 2-4;
preferably, the boron nitride is hexagonal boron nitride;
the weight ratio of the boron nitride to the mixed acid solution is 1: 200-300;
the dispersion IV is ultrasonic dispersion, and the condition of the dispersion IV at least meets the following conditions: the power is 100-;
the heating IV at least satisfies the following conditions: the temperature is 60-100 ℃, and the time is 6-18 h;
the condition of the dry IV at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h.
5. The composite coating according to claim 3, wherein in the step (1), the weight ratio of the hydrophobic silicon carbide to the siloxane coupling agent II is 1: 0.1-2;
preferably, the weight ratio of the hydrophobic silicon carbide to the organic solvent III is 1: 300-500;
the preparation method of the hydrophobic silicon carbide comprises the following steps:
dispersing silicon carbide and a hydrophobic modifier in an organic solvent V to obtain a suspension, mixing the suspension with water, heating V, separating V, washing V, and drying V to obtain hydrophobic silicon carbide;
wherein the weight ratio of the hydrophobic modifier to the silicon carbide is 1: 0.1-10;
preferably, the weight ratio of the hydrophobic modifier to the organic solvent V is 1: 100-500;
preferably, the weight ratio of the suspension to the water is 100: 1-2;
the hydrophobic modifier is at least one selected from hexadecyl trimethoxy silane, hexadecyl triethoxy silane, octadecyl trimethoxy silane, octadecyl triethoxy silane, 1H,2H, 2H-perfluoro octyl triethoxy silane and 1H,1H,2H, 2H-perfluoro octyl trimethoxy silane;
the organic solvent V is at least one selected from absolute ethyl alcohol, glycerol, isobutyl alcohol, xylene, normal butyl alcohol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine;
the dispersion V is ultrasonic dispersion, and the condition of the dispersion V at least meets the following requirements: the power is 100-;
the condition of heating V at least satisfies: the temperature is 50-100 ℃, and the time is 2-6 h;
the condition of the drying V at least satisfies: the temperature is 60-100 ℃, and the time is 8-16 h.
6. The composite coating according to any one of claims 3 to 5, wherein in step (1), the condition of heating I at least satisfies: the temperature is 60-80 ℃, and the time is 2-6 h;
the condition of the drying I at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h;
the condition of heating II at least satisfies: the temperature is 60-80 ℃, and the time is 2-6 h;
the condition of drying II at least satisfies: the temperature is 60-100 ℃, and the time is 6-24 h;
the siloxane coupling agent I and the siloxane coupling agent II are each independently selected from at least one of KH540, KH-550, KH-560 and KH-570.
7. The composite coating according to any one of claims 3 to 5, wherein in step (2), the weight ratio of the coupling agent grafted silicon carbide to the coupled grafted boron nitride is 1:0.1 to 10;
preferably, the weight ratio of the coupling agent grafted silicon carbide to the coupling grafted boron nitride is 1: 0.5-5;
the method for dispersing III comprises the following steps: ultrasonically dispersing the coupling agent grafted silicon carbide and the coupling grafted boron nitride in the same organic solvent respectively, wherein the power of ultrasonic dispersion is 100-20W, and the time of ultrasonic dispersion is 40-90min each time;
preferably, the weight ratio of the coupled grafted silicon carbide to the organic solvent IV is 1: 100-500;
the condition of heating III at least satisfies: the temperature is 50-90 ℃ and the time is 2-6 h;
the condition of drying III at least satisfies: the temperature is 50-70 ℃, and the time is 6-24 h;
preferably, the organic solvent II, the organic solvent III and the organic solvent IV are each independently selected from at least one of absolute ethanol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine.
8. The composite coating according to any of claims 1-5, characterized in that the epoxy resin is selected from at least one of CYD-011, CYD-014, E44, E20 and ES-020;
the organic solvent I is at least one selected from absolute ethyl alcohol, glycerol, isobutanol, xylene, n-butanol, styrene, perchloroethylene, trichloroethylene, ethylene glycol ether and triethanolamine;
the auxiliary agent is at least one of defoaming agent, dispersing agent and accelerating agent;
the defoaming agent is at least one of polyether modified organic silicon defoaming agent, isocyanate modified organic silicon defoaming agent, higher alcohol fatty acid ester defoaming agent and fatty amide defoaming agent;
the dispersing agent is selected from at least one of polyacrylate, butyl ester, N-methyl pyrrolidone, dimethyl formamide and stearic acid monoglyceride;
the accelerator is a fatty amine accelerator and/or an acid anhydride accelerator;
the aliphatic amine accelerator is at least one of 2,4, 6-tri (dimethylaminomethyl) phenol, EP-184 and triethanolamine, and the acid anhydride accelerator is N, N-dimethylbenzylamine and/or 1, 8-diazabicyclo-bicyclo (5,4,0) -7-undecene;
preferably, the auxiliary agents are defoaming agents, dispersing agents and accelerating agents; the weight ratio of the defoaming agent to the dispersing agent to the accelerating agent is 1:0.5-2: 2-5.
9. A method for preparing a composite coating according to any one of claims 1 to 8, characterized in that it comprises the following steps:
s1, uniformly mixing the hydrophobic siloxane/boron nitride compound, the epoxy resin, the auxiliary agent and the organic solvent I to obtain a mixture;
s2, ball-milling the mixture obtained in the step (1) to obtain the composite coating.
10. The method for preparing a composite coating according to claim 9, characterized in that: in step S2, the ball milling conditions at least satisfy: the rotation speed is 500-2000rpm, the temperature is 40-100 ℃, and the time is 4-24 h.
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