CN116200098B - Wear-resistant high-hardness powder coating and preparation method thereof - Google Patents

Wear-resistant high-hardness powder coating and preparation method thereof Download PDF

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CN116200098B
CN116200098B CN202310130161.1A CN202310130161A CN116200098B CN 116200098 B CN116200098 B CN 116200098B CN 202310130161 A CN202310130161 A CN 202310130161A CN 116200098 B CN116200098 B CN 116200098B
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CN116200098A (en
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邓环
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Guangdong Inking Technology Co ltd
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • 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
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a wear-resistant high-hardness powder coating and a preparation method thereof, belonging to the technical field of powder coatings, and comprising the following raw materials in parts by weight: 100 parts of matrix resin, 7-8 parts of modified filler, 3-4 parts of photoinitiator, 0.8-1 part of defoaming agent and 1.1-1.3 parts of leveling agent; the matrix resin and the modified filler are used as main raw materials, so that the product performance is improved, and the obtained product has stable mechanical properties, good wear resistance and excellent apparent properties. The POSS grafted graphene is selected as a base material of the modified filler, on one hand, the POSS grafted graphene has better dispersibility relative to single graphene oxide, and on the other hand, the POSS grafted graphene has good mechanical property and toughening effect as an organic-inorganic hybrid material, and is grafted on the graphene oxide, so that the microcrack can be prevented from expanding. And the hardness and the wear resistance of the coating after curing are improved by adjusting the components of the matrix resin.

Description

Wear-resistant high-hardness powder coating and preparation method thereof
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a wear-resistant high-hardness powder coating and a preparation method thereof.
Background
The powder coating is a solid powder synthetic resin coating composed of solid resin, pigment, filler, auxiliary agent and the like. Has the characteristics of no solvent pollution, 100 percent film formation and low energy consumption. Powder coatings are of two general classes, thermoplastic and thermosetting. The thermosetting powder paint uses thermosetting synthetic resin as filming matter, and the resin is first molten and then chemically cross-linked to form smooth hard film. Various raw materials are added into the raw materials to meet various performance requirements, and the requirements of product coating are met.
The traditional powder coating is used for covering the surface of the appearance part to form a coating, the coating is prepared by adopting a one-time spraying and one-time film forming process, and the coating has the defects of high bonding strength to a base material, good high temperature resistance and low hardness. In the using process of the coating coated with the traditional powder coating, the appearance effect and the service life can be seriously affected when the coating is worn or scratched by external force; in the prior art, a high-hardness inorganic compound is added into a resin main body material to improve the wear resistance of a coating, for example, chinese patent CN107254249A discloses a high-hardness powder coating, a preparation method and application thereof, and the requirement of a base material on the hardness performance is met by adding a filler, but the filler is easy to form pinholes in the coating to influence the covering property of the coating.
Disclosure of Invention
The invention aims to provide a wear-resistant high-hardness powder coating and a preparation method thereof, which are used for solving the problems in the background technology.
The aim of the invention can be achieved by the following technical scheme:
the wear-resistant high-hardness powder coating comprises the following raw materials in parts by weight:
100 parts of matrix resin, 7-8 parts of modified filler, 3-4 parts of photoinitiator, 0.8-1 part of defoaming agent and 1.1-1.3 parts of leveling agent; the modified filler is prepared by the following steps:
mixing POSS grafted graphene and N, N-dimethylformamide, setting the temperature to 20 ℃, adding octenyl succinic anhydride, stirring and reacting for 3 hours, and filtering and drying after the reaction is finished to obtain the modified filler. Wherein, the dosage ratio of the POSS grafted graphene, the N, N-dimethylformamide and the octenyl succinic anhydride is 5g:100mL:1g. In order to improve the dispersibility of POSS grafted graphene, octenyl succinic anhydride is used as a raw material to perform grafting reaction on the POSS grafted graphene, so that the graphene oxide has a stable structure and good chemical stability and mechanical property, can be used as a filler to improve the strength, hardness and wear resistance of a coating, and can be used as a corrosion-resistant material to prevent penetration of a corrosive medium.
Further, the POSS grafted graphene is prepared by the following steps:
mixing graphene oxide with methanol, performing ultrasonic dispersion on the mixture for 30min to obtain a dispersion liquid a, mixing amino-POSS with methanol, performing ultrasonic dispersion on the mixture for 30min to obtain a dispersion liquid b, mixing the dispersion liquid a and the dispersion liquid b, adding phosphorus pentoxide, setting the temperature at 60 ℃ after the addition, performing reflux stirring for 8h, and performing centrifugal separation and deionized water washing after the reaction is finished to obtain POSS grafted graphene. The amino-POSS is octaamino cage polysilsesquioxane. Wherein, the dosage ratio of graphene oxide to methanol in the dispersion liquid a is 0.1g:20mL; the ratio of amino-POSS to methanol in dispersion b was 0.1g:10mL; the volume ratio of dispersion a to dispersion b was 2:1, a step of; the dosage mass of the phosphorus pentoxide and the graphene oxide is 10:1. and (3) reacting carboxyl on the graphene oxide with amino on the amino-POSS to generate an amide bond, so as to obtain the POSS grafted graphene.
Further, the matrix resin comprises a modified epoxy resin and a polyurethane resin; mass ratio of modified epoxy resin to polyurethane resin 7:3.
further, the modified epoxy resin is prepared by the steps of:
mixing bisphenol A epoxy resin E-12, tetramethyl ammonium chloride and epoxy chloropropane under the protection of nitrogen, stirring and mixing at the temperature of 60 ℃, adding 30% sodium hydroxide aqueous solution by mass, heating to 80 ℃ after the addition, preserving heat and reacting for 4 hours, and distilling under reduced pressure to remove water and unreacted epoxy chloropropane after the reaction is finished to obtain an intermediate product;
step two, mixing the intermediate product with toluene under the protection of nitrogen, adding a mixture of tetrabutylammonium bromide, hydroquinone and N-isopropyl maleimide acid at the temperature of 90 ℃, heating to 110 ℃ after the addition, and reacting until the acid value is reduced to 5mgKOH/g -1 And (3) distilling under reduced pressure to separate the solvent, and drying to obtain the modified epoxy resin. The modified epoxy resin is prepared by adding epoxy functional groups under the catalysis of sodium hydroxide and tetramethyl ammonium chloride serving as raw materials of bisphenol A epoxy resin, and then reacting with N-isopropyl maleimide acid under the catalysis of tetrabutyl ammonium bromide to introduce double bonds. The imine ring structure is introduced through the N-isopropyl acid group maleimide acid, so that the modified epoxy resin has good heat resistance and the wear resistance of the cured coating is improved.
Further, the dosage ratio of bisphenol A type epoxy resin E-12, tetramethyl ammonium chloride, epichlorohydrin and sodium hydroxide aqueous solution in the first step is 10g:0.1g:3g:4mL;
in the second step, the adding amount of tetrabutylammonium bromide is 3% of the mass of the intermediate product, and the adding amount of hydroquinone is 0.01% of the intermediate product; the ratio of the intermediate, N-isopropylmaleimide acid and toluene was 10g:3.6g:100mL.
N-isopropylacid maleimide acid is prepared by the steps of:
maleic anhydride and D, L-aminopropionic acid are mixed according to a molar ratio of 1:1 adding the mixture into glacial acetic acid, stirring the mixture at the temperature of 30 ℃ for reaction for 5 hours, and after the reaction is finished, filtering and drying the obtained reactant, and recrystallizing the obtained reactant by using methanol to obtain the N-isopropyl maleimide. Glacial acetic acid is used as a solvent, and the dosage ratio of the glacial acetic acid to the maleic anhydride is 10mL:1g.
The polyurethane resin is prepared by the following steps:
and (3) stirring the m-xylylenediamine, isophorone diamine, 1, 3-cyclohexanediamine, polyether amine D230 and trimethylolpropane triacrylate for 30min to be uniform, heating to 85 ℃ under stirring, and preserving the temperature for 4-5h to obtain the polyurethane resin. The dosage mass ratio of the xylylenediamine, isophoronediamine, 1, 3-cyclohexanediamine, polyetheramine D230 and trimethylolpropane triacrylate is 4:4:1:5:2. in order to further improve the surface defects of the epoxy resin caused by the overlarge crosslinking density, a proper amount of thermoplastic resin is added, and the polyurethane resin is inserted into a network of the epoxy resin, so that the epoxy resin has better toughness and ductility.
Further, the photoinitiator is formed by mixing dimethyl benzil ketal and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide with the same mass.
Further, the defoaming agent is benzoin; the leveling agent is PV88.
The preparation method of the wear-resistant high-hardness powder coating comprises the following steps of weighing raw materials in parts by weight:
weighing raw materials according to parts by weight, mixing the weighed raw materials, adding the weighed raw materials into a single screw extruder for melt mixing extrusion, cooling, crushing and sieving with a 400-mesh sieve after extrusion to obtain the wear-resistant high-hardness powder coating.
Further, the temperature of zone I is controlled in the range of 70-80 ℃ and the temperature of zone I I is controlled in the range of 85-90 ℃ during melt mixing. When in melt mixing, the mixing temperature is controlled, so that the mixing effect of raw materials is poor when the temperature is too low, and the effect of influencing the product performance due to solidification reaction caused by too high mixing temperature is prevented.
The invention has the beneficial effects that:
the invention uses the matrix resin and the modified filler as main raw materials, improves the product performance, and the obtained product has stable mechanical property, good wear resistance and excellent apparent performance.
According to the invention, POSS grafted graphene is selected as a base material of the modified filler, on one hand, the POSS grafted graphene has better dispersibility compared with single graphene oxide, and on the other hand, POSS has good mechanical property and toughening effect as an organic-inorganic hybrid material, and is grafted on the graphene oxide, so that the microcrack can be prevented from expanding. However, only untreated POSS grafted graphene is selected as modified filler, so that the modified filler is poor in dispersibility and easy to agglomerate, so that the modified filler is modified by using octenyl succinic anhydride, on one hand, the modified filler has better dispersibility, stress after curing can be uniformly distributed, on the other hand, double bonds are introduced into the dispersed filler after modification, the dispersed filler can participate in subsequent curing reaction, and the mechanical property and wear resistance of the cured coating are further improved.
According to the invention, the hardness and wear resistance of the cured coating are improved by adjusting the components of the matrix resin, and simultaneously an imine ring structure is introduced into the matrix resin for modification treatment of the modified epoxy resin, so that the heat resistance of the coating is improved, and in order to further improve the surface defects of the epoxy resin caused by overlarge crosslinking density, a proper amount of thermoplastic resin is added, and the polyurethane resin is inserted into the network of the epoxy resin, so that the coating has better toughness and ductility.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a modified epoxy resin, which is prepared through the following steps:
mixing bisphenol A epoxy resin E-12, tetramethyl ammonium chloride and epoxy chloropropane under the protection of nitrogen, stirring and mixing at the temperature of 60 ℃, adding 30% sodium hydroxide aqueous solution by mass, heating to 80 ℃ after the addition, preserving heat and reacting for 4 hours, and distilling under reduced pressure to remove water and unreacted epoxy chloropropane after the reaction is finished to obtain an intermediate product; the dosage ratio of bisphenol A epoxy resin E-12, tetramethyl ammonium chloride, epoxy chloropropane and sodium hydroxide aqueous solution is 10g:0.1g:3g:4mL;
maleic anhydride and D, L-aminopropionic acid are mixed according to a molar ratio of 1:1 adding the mixture into glacial acetic acid, stirring the mixture at the temperature of 30 ℃ for reaction for 5 hours, and after the reaction is finished, filtering and drying the obtained reactant, and recrystallizing the obtained reactant by using methanol to obtain the N-isopropyl maleimide. Glacial acetic acid is used as a solvent, and the dosage ratio of the glacial acetic acid to the maleic anhydride is 10mL:1g.
Step two, mixing the intermediate product with toluene under the protection of nitrogen, adding a mixture of tetrabutylammonium bromide, hydroquinone and N-isopropyl maleimide acid at the temperature of 90 ℃, heating to 110 ℃ after the addition, and reacting for 3 hours until the acid value is reduced to 5mgKOH/g -1 Distilling under reduced pressure to separate solvent, and drying to obtain modified epoxy resin; the adding amount of tetrabutylammonium bromide is 3% of the mass of the intermediate product, and the adding amount of hydroquinone is 0.01% of the mass of the intermediate product; the ratio of the intermediate, N-isopropylmaleimide acid and toluene was 10g:3.6g:100mL.
Comparative example 1
In this comparative example, in comparison with example 1, N-isopropylmaleimide acid was replaced with acrylic acid, and the remaining raw materials and production process were kept the same as in example 1.
Example 2
This example provides a modified filler prepared by the steps of:
mixing graphene oxide with methanol, performing ultrasonic dispersion on the mixture for 30min to obtain a dispersion liquid a, mixing amino-POSS with methanol, performing ultrasonic dispersion on the mixture for 30min to obtain a dispersion liquid b, mixing the dispersion liquid a and the dispersion liquid b, adding phosphorus pentoxide, setting the temperature at 60 ℃ after the addition, performing reflux stirring for 8h, and performing centrifugal separation and deionized water washing after the reaction is finished to obtain POSS grafted graphene. The amino-POSS is octaamino cage polysilsesquioxane. Wherein, the dosage ratio of graphene oxide to methanol in the dispersion liquid a is 0.1g:20mL; the ratio of amino-POSS to methanol in dispersion b was 0.1g:10mL; the volume ratio of dispersion a to dispersion b was 2:1, a step of; the dosage mass of the phosphorus pentoxide and the graphene oxide is 10:1.
mixing POSS grafted graphene and N, N-dimethylformamide, setting the temperature to 20 ℃, adding octenyl succinic anhydride, stirring and reacting for 3 hours, and filtering and drying after the reaction is finished to obtain the modified filler. Wherein, the dosage ratio of the POSS grafted graphene, the N, N-dimethylformamide and the octenyl succinic anhydride is 5g:100mL:1g.
Example 3
This example provides a polyurethane resin prepared by the steps of:
and (3) stirring the m-xylylenediamine, isophorone diamine, 1, 3-cyclohexanediamine, polyether amine D230 and trimethylolpropane triacrylate for 30min to be uniform, heating to 85 ℃ under stirring, and preserving the heat for 4h to obtain the polyurethane resin. The dosage mass ratio of the xylylenediamine, isophoronediamine, 1, 3-cyclohexanediamine, polyetheramine D230 and trimethylolpropane triacrylate is 4:4:1:5:2.
example 4
The wear-resistant high-hardness powder coating comprises the following raw materials in parts by weight:
weighing 100 parts of matrix resin, 7 parts of modified filler prepared in example 2, 3 parts of photoinitiator, 0.8 part of defoaming agent and 1.1 part of flatting agent according to parts by weight; mixing the weighed raw materials, adding the weighed raw materials into a single screw extruder for melt mixing extrusion, wherein the temperature of an area I is controlled within the range of 70-80 ℃ during melt mixing, and the temperature of an area I I is controlled within the range of 85-90 ℃; after extrusion, cooling, crushing and sieving with a 400-mesh sieve to obtain the wear-resistant high-hardness powder coating. The matrix resin includes the modified epoxy resin prepared in example 1 and the polyurethane resin prepared in example 3; mass ratio of modified epoxy resin to polyurethane resin 7:3. the photoinitiator is formed by mixing dimethyl benzil ketal and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide with the same mass. The deaerating agent is benzoin; the leveling agent is PV88.
Example 5
The wear-resistant high-hardness powder coating comprises the following raw materials in parts by weight:
weighing 100 parts of matrix resin, 7.5 parts of modified filler prepared in example 2, 3.5 parts of photoinitiator, 0.9 part of defoaming agent and 1.2 parts of flatting agent according to parts by weight; mixing the weighed raw materials, adding the weighed raw materials into a single screw extruder for melt mixing extrusion, wherein the temperature of an area I is controlled within the range of 70-80 ℃ during melt mixing, and the temperature of an area I I is controlled within the range of 85-90 ℃; after extrusion, cooling, crushing and sieving with a 400-mesh sieve to obtain the wear-resistant high-hardness powder coating. The matrix resin includes the modified epoxy resin prepared in example 1 and the polyurethane resin prepared in example 3; mass ratio of modified epoxy resin to polyurethane resin 7:3. the photoinitiator is formed by mixing dimethyl benzil ketal and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide with the same mass. The deaerating agent is benzoin; the leveling agent is PV88.
Example 6
The wear-resistant high-hardness powder coating comprises the following raw materials in parts by weight:
weighing 100 parts of matrix resin, 8 parts of modified filler prepared in example 2,4 parts of photoinitiator, 1 part of defoaming agent and 1.3 parts of flatting agent according to parts by weight; mixing the weighed raw materials, adding the weighed raw materials into a single screw extruder for melt mixing extrusion, wherein the temperature of an area I is controlled within the range of 70-80 ℃ during melt mixing, and the temperature of an area I I is controlled within the range of 85-90 ℃; after extrusion, cooling, crushing and sieving with a 400-mesh sieve to obtain the wear-resistant high-hardness powder coating. The matrix resin includes the modified epoxy resin prepared in example 1 and the polyurethane resin prepared in example 3; mass ratio of modified epoxy resin to polyurethane resin 7:3. the photoinitiator is formed by mixing dimethyl benzil ketal and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide with the same mass. The deaerating agent is benzoin; the leveling agent is PV88.
Comparative example 2
In this comparative example, compared to example 6, the modified filler was replaced with POSS grafted graphene in example 2, and the remaining raw materials and preparation process were kept the same as example 6.
Comparative example 3
In this comparative example, compared with comparative example 2, the modified epoxy resin was changed to the sample prepared in comparative example 1, and the remaining raw materials and preparation process were kept the same as those of comparative example 2.
Performance tests were performed on examples 4-6 and comparative examples 2-3; the air compressor is connected with the ventilation bamboo channel of the electrostatic spray gun and is powered on, the electrostatic voltage is regulated to be 50KV, the powder outlet pressure is 0.2Kg/cm, then the powder paint is added into the material hopper on the spray gun, and the distance between the spray gun head and the base material is about 15cm, and powder is sprayed. The substrate is fully melted and leveled at 120 ℃, and then is irradiated and solidified by ultraviolet light with 120W/cm illumination by a 2KW high-pressure mercury lamp.
Film hardness was measured according to the pencil test method for film hardness specified in GB/T6739-1996; film impact resistance was tested according to the film impact resistance assay specified in GB 1732-79; abrasion resistance measured according to GB/T1768-2006, abrasion resistance mg (1 kg. CS10 wheel, 1500 r); the results are shown in Table 1:
TABLE 1
Project Example 4 Example 5 Example 6 Comparative example 2 Comparative example 3
Pinhole (100 mu m film) Without any means for Without any means for Without any means for Has the following components Has the following components
Hardness of pencil 5H 5H 5H 4H 4H
Wear resistance/mg 31 29 28 41 46
Impact/(kg cm) 52.7 52.8 53.1 48.7 46.5
As can be seen from Table 1, the powder coating prepared by the invention has higher hardness and better wear resistance when in use, and probably because the filler treated in the dispersing effect can be better dispersed, and a more stable structure can be formed in the curing process, and the wear resistance and the impact resistance are better.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (5)

1. The wear-resistant high-hardness powder coating is characterized by comprising the following raw materials in parts by weight: 100 parts of matrix resin, 7-8 parts of modified filler, 3-4 parts of photoinitiator, 0.8-1 part of defoaming agent and 1.1-1.3 parts of leveling agent; the modified filler is prepared by the following steps:
mixing POSS grafted graphene and N, N-dimethylformamide, setting the temperature to 20 ℃, adding octenyl succinic anhydride, stirring for reaction for 3 hours, and filtering and drying after the reaction is finished to obtain modified filler; wherein, the dosage ratio of the POSS grafted graphene, the N, N-dimethylformamide and the octenyl succinic anhydride is 5g:100mL:1g;
the matrix resin comprises modified epoxy resin and polyurethane resin; mass ratio of modified epoxy resin to polyurethane resin 7:3, a step of;
the POSS grafted graphene is prepared through the following steps:
mixing graphene oxide with methanol, performing ultrasonic dispersion for 30min to obtain a dispersion liquid a, mixing amino-POSS with methanol, performing ultrasonic dispersion for 30min to obtain a dispersion liquid b, mixing the dispersion liquid a and the dispersion liquid b, adding phosphorus pentoxide, setting the temperature at 60 ℃ after the addition, performing reflux stirring for 8h, performing centrifugal separation after the reaction is finished, and washing with deionized water to obtain POSS grafted graphene; the amino-POSS is octaamino cage polysilsesquioxane;
the modified epoxy resin is prepared by the following steps:
mixing bisphenol A epoxy resin E-12, tetramethyl ammonium chloride and epoxy chloropropane under the protection of nitrogen, stirring and mixing at the temperature of 60 ℃, adding 30% sodium hydroxide aqueous solution by mass, heating to 80 ℃ after the addition, and carrying out heat preservation reaction for 4 hours to obtain an intermediate product;
and step two, mixing the intermediate product with toluene under the protection of nitrogen, adding a mixture of tetrabutylammonium bromide, hydroquinone and N-isopropyl maleimide acid at the temperature of 90 ℃, heating to 110 ℃ after the addition, and reacting to obtain the modified epoxy resin.
2. The wear-resistant high-hardness powder coating according to claim 1, wherein the photoinitiator is prepared by mixing benzil dimethyl ketal, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and the like.
3. A wear resistant high hardness powder coating according to claim 1, wherein the de-bubbling agent is benzoin; the leveling agent is PV88.
4. The method for preparing the wear-resistant high-hardness powder coating according to claim 1, wherein the raw materials are mixed, the weighed raw materials are added into a single screw extruder for melt mixing extrusion, and the powder coating is obtained after cooling, crushing and sieving with a 400-mesh sieve.
5. The method for producing a wear-resistant high-hardness powder coating according to claim 4, wherein the temperature in zone I is controlled in the range of 70 to 80℃and the temperature in zone II is controlled in the range of 85 to 90℃during melt mixing.
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