A graphene-coated aluminum silver powder paint, a preparation method thereof, and a use method thereof

Abstract

The present application relates to a kind of graphene-coated aluminum silver powder paint, its preparation method and its use method, it relates to the technical field of paint, wherein a kind of graphene-coated aluminum silver powder paint, including A component and B component, A component: epoxy resin 26~33, xylene 13~17, n-butanol 13~17, organic-inorganic double-coated aluminum silver paste 13~17, sericite 4~6, aluminum tripolyphosphate 17~22, fumed silica 1, leveling agent 0.1, defoaming agent 0.05, B component: hexahydrophthalic anhydride 50, acid anhydride accelerator 2, xylene 24, n-butanol 24, the paint of the present application can play the role of heat dissipation, also has the effect of corrosion prevention.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to a kind of graphene coated aluminum silver powder, its preparation method and its application in coating. BACKGROUND

[0002] Anticorrosive coating is extremely important in industrial applications, but there is a contradiction between thermal conductivity and corrosion resistance in traditional coatings. In order to solve this problem, graphene, with its unique physical and chemical properties, has become an ideal choice to improve the performance of coatings. Graphene has excellent adhesion, water resistance, hardness and stability, and can remain stable in high temperature and corrosive environments.

[0003] Chinese patent application with publication number CN109233565A and publication date January 18, 2019 proposes a heavy-duty graphene-modified epoxy zinc-rich coating and its manufacturing method, which discloses a heavy-duty graphene-modified epoxy zinc-rich coating made from the following raw materials by weight percentage: epoxy resin 18-25wt%, anti-settling agent 1.5-3wt%, organic solvent 12-16wt%, coated aluminum silver paste 1-3wt%, functional filler 10-25wt%, nano-sized graphene additive 0.1-0.5wt%, functional additive 0.2-0.5wt%, modified fatty amine curing agent 12-16wt%, and the rest is zinc powder.

[0004] The strong physical shielding layer formed by the two-dimensional sheet structure of the coated aluminum silver paste combined with graphene substantially improves the performance in terms of weather resistance, delays the powdering of the epoxy coating, and thus prolongs the recoating time of the matching coating, making the coating have better workability and construction performance.

[0005] For the above technical solution, although this material improves the weather resistance of the coating, the aluminum silver paste and graphene are only simply mechanically mixed, and the addition of only two can only exert their own characteristics, which is insufficient in terms of improving the weather resistance and strength of the coating, and also does not improve the heat dissipation performance of the material. SUMMARY

[0006] In order to further improve the weather resistance and heat dissipation performance of the coating, the present application provides a kind of graphene coated aluminum silver powder, its preparation method and its application in coating.

[0007] In the first aspect, the present application provides a kind of graphene coated aluminum silver powder coating, which adopts the following technical solution:

[0008] A kind of graphene coated aluminum silver powder coating, comprising the following components and their weight fractions:

[0009] The A component: epoxy resin 26~33, xylene 13~17, n-butanol 13~17, organic and inorganic double coated aluminum silver paste 13~17, sericite 4~6, aluminum tripolyphosphate 17~22, fumed silica 1, leveling agent 0.1, defoaming agent 0.05, the aluminum silver paste of the organic and inorganic double coated aluminum silver paste is graphene coated aluminum silver paste, the graphene coated aluminum silver paste comprises graphene coated aluminum silver powder, the leveling agent is polyether modified silicone leveling agent, and the defoaming agent is polyether modified silicone defoaming agent;

[0010] The B component: hexahydrophthalic anhydride 50, anhydride accelerator 2, xylene 24, n-butanol 24.

[0011] By adopting the above technical scheme, the graphene has very high electron mobility and can quickly conduct electrons, so that a conductive network can be formed in the coating, when the aluminum silver powder conductive particles in the coating are oxidized to cause the conductivity to decrease, the graphene can serve as a conductive bridge to maintain the electrochemical protection effect of the coating, the graphene has very good heat conduction performance, the addition of the graphene can improve the heat dissipation effect, the graphene has high chemical stability and is not easy to be corroded by corrosive media, so that the corrosion resistance of the coating can be maintained for a long time; the graphene has strong hydrophobicity and can form a water barrier layer on the surface of the coating to prevent water molecules in the air from entering the surface of the workpiece, thereby enhancing the protection of the workpiece.

[0012] The aluminum silver powder can reflect ultraviolet rays, infrared rays and visible light, has a heat dissipation effect on sunlight, and can form a dense aluminum oxide film by reacting with oxygen to protect the aluminum from further oxidation.

[0013] However, the aluminum powder is easy to react with water and oxygen, which reduces or even eliminates its excellent performance, and surface coating and modification of the aluminum powder are of great significance to improve its stability in corrosive media, the coated aluminum silver paste has better acid and alkali resistance and ultraviolet resistance than the uncoated aluminum silver paste.

[0014] Optionally, the epoxy resin is alicyclic epoxy resin.

[0015] By adopting the above technical scheme, the alicyclic epoxy resin can form a compact and rigid molecular structure because the epoxy group is directly connected to the alicyclic ring, and the crosslinking density is high after curing, so that the heat distortion temperature is high, which is different from ordinary bisphenol A type epoxy resin, and the molecular structure of the alicyclic epoxy resin does not contain benzene ring, so it has good weather resistance and ultraviolet radiation resistance. At the same time, the reactivity of the alicyclic epoxy resin to anhydride is greater than that to amine, and it can be fully cured in an anhydride system, which can avoid the use of amine curing agent with high toxicity and high volatility, and is safer for operators.

[0016] In a second aspect, the application provides a preparation method of graphene-coated aluminum silver powder paint, which adopts the following technical scheme:

[0017] A preparation method of graphene-coated aluminum silver powder paint, comprising the following steps:

[0018] S1, preparing graphene-coated aluminum silver powder:

[0019] S11, adding graphene oxide powder into deionized water, the sheet thickness of the graphene oxide is 1-10 nanometers, the diameter is 1-10 micrometers, ultrasonic dispersion is performed for 30-120 minutes, the ultrasonic frequency is 50-100 KHz, and graphene oxide dispersion liquid is prepared, the concentration of the graphene oxide dispersion liquid is 1-100 g / L;

[0020] S12, adding aluminum silver powder into the graphene oxide dispersion liquid, the particle size of the aluminum silver powder is 1-100 micrometers, and the mass ratio of the graphene oxide to the aluminum silver powder in the graphene oxide dispersion liquid is 1: (100-1000);

[0021] S13, adjusting the pH value of the graphene oxide dispersion liquid by using sulfuric acid or hydrochloric acid, and performing reaction under room temperature, continuously stirring is performed by using a stirring device during the reaction, the stirring speed is 10-60 r / min, and the pH value is 1-6;

[0022] S14, after the reaction is completed, the obtained product is washed, suction filtered, and dried in an oven until completely dry, and graphene-coated aluminum silver powder is prepared.

[0023] S2, preparing graphene-coated aluminum silver paste:

[0024] S21, taking 100 parts of the graphene-coated aluminum silver powder, 100 parts of D80 solvent oil and 1 part of fatty acid, mixing and grinding in a ball mill for 5 hours to obtain a mixed paste;

[0025] S22, filtering the mixed paste in a vibrating screen with a mesh size of 250, and then adding the filtered mixed paste into a filter press to squeeze graphene-coated aluminum silver paste filter cake;

[0026] S23, uniformly stirring the graphene-coated aluminum silver paste filter cake in a stirrer to obtain graphene-coated aluminum silver paste.

[0027] S3, preparing organic-inorganic double-coated aluminum silver paste:

[0028] S31, dispersion: dispersing the graphene-coated aluminum silver paste in a mixed solvent of ethanol and water to obtain a uniform precursor; the volume ratio of the ethanol to the water is 1:1, and the addition amount of the mixed solvent of the ethanol and the water is 350% of the weight of the aluminum silver paste;

[0029] S32, inorganic coating: the above precursor is dropped into tetraethyl orthosilicate within 1 hour and stirred and heated, and the temperature of the whole system is controlled at 60-70℃, under the catalysis of ammonia, hydrolysis reaction is caused, after completion, cooling, washing, filtering, inorganic silica-coated / graphene-coated aluminum silver paste is obtained; tetraethyl orthosilicate is used as the precursor of silicon dioxide, the amount of addition is 40% of the weight of the aluminum silver paste; the amount of addition of ammonia is 10% of the weight of the aluminum silver paste;

[0030] S33, organic coating: add toluene to a round-bottom flask with a stirrer, a dropping funnel and a reflux condenser, disperse the above inorganic silica-coated aluminum silver paste in toluene, the amount of addition of toluene is 350% of the weight of the aluminum silver paste; then stir thoroughly for 30 minutes, successively add silane coupling agent and azobisisobutyronitrile, the amount of addition of the silane coupling agent is 2% of the weight of the inorganic silica-coated aluminum silver paste, the amount of addition of the azobisisobutyronitrile is 2% of the weight of the inorganic silica-coated aluminum silver paste, vacuumize the system, pass inert gas, repeat three times, and keep the whole reaction process in the protection of continuous inert gas atmosphere, place the round-bottom flask in a water bath pot and heat to 70℃, then drop the fluorine-containing propylene acrylate monomer, the amount of addition of the fluorine-containing propylene acrylate monomer is 50% of the weight of the inorganic silica-coated aluminum silver paste; drop for 1 hour; after the temperature of the system is raised to 85℃, continue to react for 4 hours, cool, wash, filter, and the organic and inorganic double-coated aluminum silver paste is obtained.

[0031] S4, preparation of super-weather-resistant graphene anticorrosive heat dissipation coating:

[0032] Preparation method of component A:

[0033] Add xylene and n-butanol to a stirring tank, turn on the high-speed disperser, rotate at a speed of 500-700 r / min, and uniformly mix the solvents for 1-10 min;

[0034] After adding the alicyclic epoxy resin to the uniformly mixed solvents, adjust the rotating speed to 1500-2000 r / min, heat under the condition of 50-100℃, and after the alicyclic epoxy resin is completely dissolved, mixture A is obtained;

[0035] Add the organic and inorganic double-coated aluminum silver paste, sericite, aluminum tripolyphosphate and fumed silica to mixture A, disperse at 1500-2000 r / min for 2-3 hours, test the fineness with a doctor blade fineness gauge, and the fineness is less than 20 μm, to obtain mixture B;

[0036] Adjust the rotating speed to 800-1000 r / min, add the leveling agent and defoaming agent to mixture B, stir for 10-15 min, filter with 200-mesh filter cloth, and package.

[0037] Preparation method of component B:

[0038] In the stirring tank, add xylene, n-butanol, hexahydrophthalic anhydride and acid anhydride accelerator, the stirring speed is 800-1000r / min, after the hexahydrophthalic anhydride and acid anhydride accelerator are completely dissolved, filter with a 300 mesh filter screen, and then sub-pack.

[0039] By adopting the technical scheme, the aluminum-silver powder can react with sulfuric acid or hydrochloric acid to generate aluminum-hydrogen bond, the aluminum-hydrogen bond has strong reducing capacity, and the graphene oxide can be reduced to graphene on the surface of the aluminum-silver in situ.

[0040] Al + H ＋ → Al 3＋ + H2→ Al 3＋ + 2·H→ Al-H (aluminum-hydrogen bond)

[0041] Al-H + GO (graphene oxide) → Al-RGO (graphene on the surface of the aluminum-silver in situ reduction) + ·H

[0042] Compared with the simple mechanical stirring mixing of adding graphene directly into the coating system, the method of graphene-coated aluminum-silver makes the graphene uniform and the graphene and the aluminum-silver combine firmly, so that the graphene and the aluminum-silver can form a uniform and close conductive network in the coating, improve the electrochemical protection effect of the coating, and thus improve the corrosion resistance.

[0043] Meanwhile, the hexahydrophthalic anhydride is used as an epoxy resin curing agent, if the AB components are not separated, the coating will be cured before use, and after the AB components are separated, the coating can be mixed according to the proportion and used immediately, and the coating is cured on the surface of the workpiece after spraying.

[0044] Optionally, the mass ratio of the graphene oxide to the aluminum-silver powder in the graphene oxide dispersion liquid in S12 is 1: (500-800).

[0045] By adopting the technical scheme, within this range, the aluminum-silver is basically coated with graphene, and there is no excessive aluminum-silver or graphene; below this range, there is more graphene than aluminum-silver, and the aluminum-silver is basically coated, but there is more residual graphene; and above this range, there is more aluminum-silver than graphene, and part of the aluminum-silver is not coated.

[0046] Optionally, the pH range in S13 is 1-4.

[0047] By adopting the technical scheme, the lower the pH is, the higher the hydrogen ion content is, the more aluminum-hydrogen bonds are generated, and the rate of reducing the graphene oxide is faster and more sufficient.

[0048] In a third aspect, the application provides a use method of the graphene-coated aluminum-silver powder coating, which adopts the following technical scheme:

[0049] A method for using a graphene-coated aluminum silver powder coating, comprising the following steps:

[0050] Pre-treatment: the metal surface is pre-treated, and the surface of the coated object is subjected to sand blasting, degreasing and rust removal, washing, phosphating, passivation, deionized water washing, drying of the phosphating film, and elimination of oil stains and dust on the surface;

[0051] Spraying: the A component and the B component are mixed in a ratio of 1:0.5, and sprayed on the workpiece;

[0052] Curing: after spraying, the workpiece is air-dried for 10-20 minutes in a 30 DEG C environment, and then placed in a 120-150 DEG C environment for curing for 1 hour, and polished with 240 mesh sandpaper.

[0053] By adopting the above technical scheme, the graphene-coated aluminum silver powder coating can be sprayed onto the metal surface.

[0054] Optionally, a secondary spraying and curing step is added after the curing step,

[0055] Secondary spraying and curing: according to the same spraying and curing steps described above, secondary spraying and curing are performed.

[0056] By adopting the above technical scheme, since thick spraying in the first spraying step can cause sagging, poor defoaming, and difficulty in volatilizing the solvent in the bottom layer, the coating surface will have many defects, and the secondary spraying can cover the coating defects, so the two-coating process is adopted, and the dry film thickness reaches 80-100 mu m

[0057] In summary, the present application has at least one of the following beneficial technical effects:

[0058] 1. The heat dissipation anticorrosive coating of the present application can not only dissipate heat but also has anticorrosive effect, and is very suitable for use in fields requiring heat dissipation in the ocean.

[0059] 2. The aliphatic epoxy resin used in the present application has excellent anticorrosive properties, and the combination of the aliphatic epoxy resin and graphene has a synergistic effect, which amplifies the anticorrosive properties and provides excellent anticorrosive properties. DETAILED DESCRIPTION

[0060] The present application will be further described in detail below in conjunction with examples.

[0061] In the specific embodiments of the present application, the reagents and instruments used in the following examples can be purchased as commodities.

[0062] The high molecular epoxy resin is a multi-functional aliphatic epoxy resin EPHE3150 from Japan Daiso.

[0063] The xylene is xylene with a purity of ≥99.0% from the National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0064] n-butanol is n-butanol ≥ 99.0% from Sinopharm Chemical Reagent Co., Ltd.

[0065] sericite is GA-6 from Anhui Gei New Material Technology Co., Ltd., with an average particle size of 15 ± 1.5 μm, an oil absorption value of 35-42 g / 100g, and a pH value of 4-7.

[0066] aluminum tripolyphosphate is aluminum tripolyphosphate APW-1 from Changzhou Akzo New Materials Technology Co., Ltd., with an oil absorption value of 35-45 g / 100g.

[0067] fumed silica is WACKER AEROSIL ® 200, a hydrophilic fumed silica with a specific surface area (BET) of 175-225 m² / g, suitable for a variety of applications.

[0068] leveling agent is BYK-333 silicone leveling agent from BYK CHEMICAL, and TEGO-450 silicone leveling agent from DEGOREX.

[0069] defoaming agent is BYK-077 silicone defoaming agent from BYK CHEMICAL, and TEGO Foamex N silicone defoaming agent from DEGOREX.

[0070] hexahydrophthalic anhydride is hexahydrophthalic anhydride ≥ 99.0% from Sinopharm Chemical Reagent Co., Ltd.

[0071] anhydride accelerator is non-yellowing anhydride accelerator H-600 from Chuzhou Huisheng Electronic Material Co., Ltd.

[0072] Example 1: This example discloses a super-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0073] Component A: alicyclic epoxy resin 28.11, dimethylbenzene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05,

[0074] Component B: hexahydrophthalic anhydride 50, anhydride accelerator 2, dimethylbenzene 24, n-butanol 24.

[0075] The preparation method is as follows,

[0076] S1, preparation of graphene-coated aluminum silver powder:

[0077] S11, add graphene oxide powder into deionized water, ultrasonic dispersion for 60 min, ultrasonic frequency is 80 KHz, prepare graphene oxide dispersion liquid, the sheet thickness of the graphene oxide is 1-10 nanometers, the diameter is 1-10 μm, the concentration of the graphene oxide dispersion liquid is 50 g / L;

[0078] S12, add aluminum silver powder into the graphene oxide dispersion liquid, the particle size range of the aluminum silver powder is 1-100 μm, the mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion liquid is 1:650;

[0079] S13, use sulfuric acid or hydrochloric acid to adjust the pH value of the graphene oxide dispersion liquid, carry out the reaction under room temperature, continuously stir in the stirring device during the reaction, the stirring speed range is 30 r / min, the pH value is 1;

[0080] S14, after the reaction is completed, wash, filter and dry the obtained product in the oven until completely dry, prepare graphene coated aluminum silver powder.

[0081] S2, prepare graphene coated aluminum silver paste:

[0082] S21, take 100 parts of the graphene coated aluminum silver powder, 100 parts of D80 solvent oil and 1 part of fatty acid, add into the ball mill to carry out mixing and grinding for 5 h to obtain mixed paste;

[0083] S22, add the mixed paste into the vibrating screen with 250 mesh to carry out filtration, add the filtered mixed paste into the filter press to squeeze into graphene coated aluminum silver paste filter cake;

[0084] S23, add the graphene coated aluminum silver paste filter cake into the stirrer to stir uniformly to obtain graphene coated aluminum silver paste.

[0085] S3, prepare organic and inorganic double coated aluminum silver paste:

[0086] S31, dispersion: disperse the graphene coated aluminum silver paste into the mixed solvent of ethanol and water to obtain uniform precursor; the volume ratio of the ethanol and water is 1:1, the added amount of the mixed solvent of ethanol and water is 350% of the weight of the aluminum silver paste;

[0087] S32, inorganic coating: drop the above-mentioned precursor into tetraethyl orthosilicate within 1 hour, stir and heat and control the temperature of the whole system at 60-70℃, under the catalysis of ammonia water, make it hydrolyze, after completion, cool, wash, filter to obtain inorganic silicon dioxide coated / graphene coated aluminum silver paste; the added amount of the tetraethyl orthosilicate as the precursor of silicon dioxide is 40% of the weight of the aluminum silver paste; the added amount of the ammonia water is 10% of the weight of the aluminum silver paste;

[0088] S33, organic coating: add toluene to a round bottom flask with a stirrer, dropping funnel, reflux condenser, disperse the inorganic silica-coated aluminum silver paste in toluene, the amount of toluene added is 350% of the weight of the aluminum silver paste; then stir for 30 minutes, add silane coupling agent and azobisisobutyronitrile in turn, the amount of silane coupling agent added is 2% of the weight of the inorganic silica-coated aluminum silver paste, the amount of azobisisobutyronitrile added is 2% of the weight of the inorganic silica-coated aluminum silver paste, vacuumize the system, pass inert gas, repeat three times, and keep the whole reaction process in a continuous inert gas atmosphere, place the round bottom flask in a water bath and heat to 70°C, then add fluorine-containing acrylate monomer dropwise, the amount of fluorine-containing acrylate monomer added is 50% of the weight of the inorganic silica-coated aluminum silver paste; 1 hour for dropwise addition; after the temperature of the system is raised to 85°C, continue to react for 4 hours, cool, wash, filter, and the organic-inorganic double-coated aluminum silver paste is obtained.

[0089] S4, preparation of super-weather-resistant graphene anticorrosion heat dissipation paint:

[0090] A component preparation method:

[0091] Add xylene and n-butanol to the stirring tank, turn on the high-speed disperser at a speed of 600 r / min, and mix uniformly for 5 min to obtain a uniform mixture of solvents;

[0092] Add the alicyclic epoxy resin to the uniform mixture of solvents, adjust the stirring speed to 1600 r / min, heat at 80°C, and wait for the alicyclic epoxy resin to completely dissolve to obtain mixture A;

[0093] Add the organic-inorganic double-coated aluminum silver paste, sericite, aluminum tripolyphosphate, and fumed silica to mixture A, disperse at 1600 r / min for 2.5 hours, and test the fineness with a doctor blade fineness gauge to be less than 20 μm to obtain mixture B;

[0094] Adjust the stirring speed to 800 r / min, add the leveling agent and defoaming agent to mixture B, stir for 15 min, filter with a 200-mesh filter cloth, and package separately.

[0095] B component preparation method:

[0096] Add xylene, n-butanol, hexahydrophthalic anhydride, and anhydride accelerant to the stirring tank at a stirring speed of 900 r / min, filter with a 300-mesh filter screen after the hexahydrophthalic anhydride and anhydride accelerant are completely dissolved, and package separately.

[0097] The use method is as follows,

[0098] Pre-treatment: the metal surface is pre-treated by sandblasting, degreasing and rust removal, water washing, phosphating, passivation, deionized water washing, drying of the phosphating film, and elimination of oil stains and dust on the surface of the coated object;

[0099] Spraying: mix A component and B component in the ratio of 1:0.5, spray on the workpiece;

[0100] Curing: after spraying, let the workpiece dry for 10-20 minutes in a 30℃ environment, then place the workpiece in a 120-150℃ environment for 1 hour of curing, and polish with 240 mesh sandpaper.

[0101] Second spraying and curing: follow the same spraying and curing steps as above to perform second spraying and curing.

[0102] Example 2: This example discloses an ultra-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0103] A component: alicyclic epoxy resin 26.15, dimethylbenzene 13.86, n-butanol 13.86, organic-inorganic double-coated aluminum silver paste 13.00, sericite 4.62, aluminum tripolyphosphate 17.48, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0104] The rest is exactly the same as example 1.

[0105] Example 3: This example discloses an ultra-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0106] A component: alicyclic epoxy resin 32.62, dimethylbenzene 16.75, n-butanol 16.75, organic-inorganic double-coated aluminum silver paste 17.00, sericite 5.16, aluminum tripolyphosphate 21.26, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0107] The rest is exactly the same as example 1.

[0108] Example 4: This example discloses an ultra-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0109] A component: alicyclic epoxy resin 28.11, dimethylbenzene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0110] The preparation method is as follows,

[0111] S12, the mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion liquid is 1:100.

[0112] The rest is exactly the same as example 1.

[0113] Example 5: This example discloses a super-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0114] A component: alicyclic epoxy resin 28.11, xylene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0115] The preparation method is as follows,

[0116] S12, the mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion is 1:1000.

[0117] The other is exactly the same as example 1.

[0118] Example 6: This example discloses a super-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0119] A component: alicyclic epoxy resin 28.11, xylene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0120] The preparation method is as follows,

[0121] S13, the pH range is 6.

[0122] The other is exactly the same as example 1.

[0123] Comparative Example 1: This comparative example discloses a super-weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and their weight fractions:

[0124] A component: alicyclic epoxy resin 28.11, xylene 14.05, n-butanol 14.05, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0125] A component preparation method:

[0126] Xylene and n-butanol were added to a stirring tank, and the high-speed disperser was turned on at a speed of 600 r / min for 5 min to obtain a uniform mixture of solvents;

[0127] After the alicyclic epoxy resin was added to the uniform mixture of solvents, the speed was adjusted to 1600 r / min, and heating was carried out at 80℃. After the alicyclic epoxy resin was completely dissolved, a mixture A was obtained;

[0128] Add sericite, aluminum tripolyphosphate and fumed silica into mixture A, disperse for 2.5 hours at 1600 r / min, test fineness with doctor blade fineness meter, fineness <20 μm, get mixture B;

[0129] Adjust rotation speed to 800 r / min, add leveling agent and defoaming agent into mixture B, stir for 15 min, filter with 200 mesh filter cloth, sub-pack.

[0130] The preparation method and application of component B are completely same as example 1.

[0131] Comparative example 2: this comparative example discloses a super weather-resistant graphene anticorrosive heat-dissipating coating, comprising the following components and weight fractions:

[0132] Bisphenol A epoxy resin E20 28.11, dimethylbenzene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0133] Preparation method of component A:

[0134] (2) add bisphenol A epoxy resin E20 into the uniformly mixed solvent, adjust rotation speed to 1600 r / min, heat at 80℃, until bisphenol A epoxy resin E20 is completely dissolved, get mixture A.

[0135] Other conditions are completely same as example 1.

[0136] Comparative example 3: this comparative example discloses a super weather-resistant graphene anticorrosive heat-dissipating coating, comprising the following components and weight fractions:

[0137] Component A: alicyclic epoxy resin 26.00, dimethylbenzene 13.00, n-butanol 13.00, organic-inorganic double-coated aluminum silver paste 5.00, sericite 4.00, aluminum tripolyphosphate 17.00, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0138] Other conditions are completely same as example 1.

[0139] Comparative example 4: this comparative example discloses a super weather-resistant graphene anticorrosive heat-dissipating coating, comprising the following components and weight fractions:

[0140] Component A: alicyclic epoxy resin 33.00, dimethylbenzene 17.00, n-butanol 17.00, organic-inorganic double-coated aluminum silver paste 30.00, sericite 6.00, aluminum tripolyphosphate 22.00, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0141] Other than Example 1 is exactly the same.

[0142] Comparative Example 5: This comparative example discloses a super weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and weight fractions thereof:

[0143] A component: alicyclic epoxy resin 28.11, dimethylbenzene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0144] The preparation method is as follows,

[0145] S12, the mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion liquid is 1:50.

[0146] Other than Example 1 is exactly the same.

[0147] Comparative Example 6: This comparative example discloses a super weather-resistant graphene anticorrosive heat dissipation coating, comprising the following components and weight fractions thereof:

[0148] A component: alicyclic epoxy resin 28.11, dimethylbenzene 14.05, n-butanol 14.05, organic-inorganic double-coated aluminum silver paste 14.55, sericite 4.68, aluminum tripolyphosphate 18.74, fumed silica 1, leveling agent 0.1, defoaming agent 0.05.

[0149] The preparation method is as follows,

[0150] S12, the mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion liquid is 1:1500.

[0151] Other than Example 1 is exactly the same.

[0152] The above examples, comparative examples of heat dissipation anticorrosive coating test according to GB / T 6748-2008 "marine anti-rust paint standard" test. Salt fog resistance, adhesion test with steel plate as the substrate.

[0153] 1, salt fog resistance test method: according to GB / T 1771-2007 "color paint and varnish resistance to neutral salt fog performance test" test, using Shanghai Hengding instrument equipment factory salt spray corrosion test box HDYW-90.

[0154] 2, adhesion test method: according to GB / T 5210-2006 "color paint and varnish pull-off method adhesion test standard" is determined, using dongguan lixian instrument technology co., LTD. HZ-1003B computer type servo universal material testing machine.

[0155] The UV resistance test method is according to GB / T 14522-2008 "Artificial weathering test methods for plastics, coatings, rubber materials for mechanical industry products - Fluorescent UV lamps". The UV accelerated aging equipment is a Q-LAB UV aging test box with UVA-340 lamp tube.

[0156] The heat dissipation effect test method is as follows: simulate a container, spray the heat dissipation coating of different embodiments and comparative examples on 2m, 2m, 3m iron sheet, and make them according to the same process, with the film thickness error not more than 5μm. Assemble the iron sheet into a box with 2m width, 2m height and 3m length, and place it in the same place in the open air with no shadow blocking each box in the summer sunny day with the temperature > 35℃. Place the same specification thermometer in the middle of the box 1m high from the ground. Place it in high temperature for 3 hours, and monitor the reading of the thermometer.

[0157] The test results are shown in the following table:

[0158] Salt mist resistance Adhesion Ultraviolet resistance Heat dissipation Example 1 12000h no rust, no blister, no cracking, no peeling 10.74MPa 2000h no yellowing, no powdering 39±2℃ Example 2 10600h no rust, no blister, no cracking, no peeling 9.71MPa 2000h no yellowing, no powdering 46±2℃ Example 3 11000h no rust, no blister, no cracking, no peeling 9.16MPa 2000h no yellowing, no powdering 44±2℃ Example 4 10000h no rust, no blister, no cracking, no peeling 8.96MPa 2000h no yellowing, no powdering 48±2℃ Example 5 11000h no rust, no blister, no cracking, no peeling 9.54MPa 2000h no yellowing, no powdering 44±2℃ Example 6 11200h no rust, no blister, no cracking, no peeling 9.98MPa 2000h no yellowing, no powdering 42±2℃ Comparative Example 1 400h no rust, no blister, no cracking, no peeling 10.55MPa 2000h no yellowing, no powdering 64±2℃ Comparative Example 2 12000h no rust, no blister, no cracking, no peeling 10.16MPa 100h yellowing, 500h powdering phenomenon began to appear 40±2℃ Comparative Example 3 4800h no rust, no blister, no cracking, no peeling 9.92MPa 2000h no yellowing, no powdering 56±2℃ Comparative Example 4 12000h no rust, no blister, no cracking, no peeling 4.94MPa 2000h no yellowing, no powdering 39±2℃ Comparative Example 5 8400h no rust, no blister, no cracking, no peeling 9.24MPa 2000h no yellowing, no powdering 52±2℃ Comparative Example 6 9500h no rust, no blister, no cracking, no peeling 9.81MPa 2000h no yellowing, no powdering 50±2℃

[0159] From the data comparison of Example 1 and Comparative Example 1, it can be seen that since Comparative Example 1 does not add organic-inorganic double-coated aluminum silver paste, the salt spray resistance, corrosion resistance and heat dissipation performance of Comparative Example 1 are poor.

[0160] From the data comparison of Example 1 and Comparative Example 2, it can be seen that since Comparative Example 2 only replaces the alicyclic epoxy resin with bisphenol A epoxy resin, although the salt spray resistance, adhesion and heat dissipation are not much different, the ultraviolet resistance is very poor.

[0161] From the data comparison of Example 1 and Comparative Example 3, it can be seen that since the addition ratio of the organic-inorganic double-coated aluminum silver paste of Comparative Example 3 is small, the salt spray resistance and heat dissipation are poor.

[0162] From the data comparison of Example 1 and Comparative Example 4, it can be seen that since the addition ratio of the organic-inorganic double-coated aluminum silver paste of Comparative Example 4 is large, the adhesion is poor.

[0163] From the data comparison of Example 1 and Comparative Example 5, it can be seen that since the graphene of Comparative Example 5 is too much, although the aluminum silver is basically coated, but the graphene is too much and the aluminum silver is too little in the graphene-coated aluminum silver powder, resulting in poor salt spray resistance and heat dissipation.

[0164] From the data comparison of Example 1 and Comparative Example 6, it can be seen that since the aluminum silver of Comparative Example 6 is too much, most of the aluminum silver is not coated, resulting in poor salt spray resistance and heat dissipation.

[0165] The patent can reach the effect of mutual performance enhancement by matching the cycloaliphatic epoxy resin with the graphene-coated aluminum silver, has excellent corrosion resistance and weather resistance, and can also reach the heat dissipation effect, solves the problem of frequent rework of high-temperature sea area container coating, and the problem of high temperature and poor heat dissipation of the container.

[0166] The above are preferred embodiments of the present application, not to limit the protection scope of the present application, therefore: all equivalent changes made according to the structure, shape, principle of the present application should be covered in the protection scope of the present application.

Claims

1. A graphene-coated aluminum silver powder paint, characterized by, Comprise the following components and parts by weight: A component: epoxy resin 26~33, xylene 13~17, n-butanol 13~17, organic and inorganic double coated aluminum silver paste 13~17, sericite 4~6, aluminum tripolyphosphate 17~22, fumed silica 1, leveling agent 0.1, defoaming agent 0.05, the aluminum silver paste of the organic and inorganic double coated aluminum silver paste is graphene coated aluminum silver paste, the graphene coated aluminum silver paste comprises graphene coated aluminum silver powder, the leveling agent is polyether modified silicone leveling agent, and the defoaming agent is polyether modified silicone defoaming agent; B component: hexahydrophthalic anhydride 50, anhydride accelerator 2, xylene 24, n-butanol 24; The preparation method of the organic and inorganic double coated aluminum silver paste comprises the following steps: S1, prepare graphene coated aluminum silver powder: S11, add the above graphene oxide powder to deionized water, the sheet thickness of the graphene oxide is 1~10 nanometers, the diameter is 1~10 μm, ultrasonic dispersion is carried out for 30~120 min, the ultrasonic frequency is 50~100 KHz, and graphene oxide dispersion liquid is prepared, the concentration of the graphene oxide dispersion liquid is 1~100 g / L; S12, add the above aluminum silver powder to the graphene oxide dispersion liquid, the particle size of the aluminum silver powder is 1~100 μm, and the mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion liquid is 1:100~1000; S13, adjust the pH of the graphene oxide dispersion liquid by using sulfuric acid or hydrochloric acid, and carry out reaction under room temperature conditions, continuously stirring is carried out by using a stirring device during the reaction, the stirring speed is 10~60 r / min, and the pH is 1~6; S14, after the reaction is completed, the obtained product is washed, suction filtered, and dried in an oven until completely dry, and graphene coated aluminum silver powder is prepared; S2, prepare graphene coated aluminum silver paste: S21, take 100 parts of the graphene coated aluminum silver powder, 100 parts of D80 solvent oil and 1 part of fatty acid, add them into a ball mill, mix and grind for 5 h to obtain a mixed paste; S22, add the mixed paste into a vibrating screen with a mesh size of 250 μm for filtration, and then add the filtered mixed paste into a filter press for squeezing into graphene coated aluminum silver paste filter cake; S23, add the graphene coated aluminum silver paste filter cake into a stirrer, stir uniformly to obtain graphene coated aluminum silver paste; S3, prepare organic and inorganic double coated aluminum silver paste: S31, dispersion: disperse the above graphene coated aluminum silver paste in a mixed solvent of ethanol and water to obtain a uniform precursor; the volume ratio of the ethanol and water is 1:1, and the addition amount of the mixed solvent of ethanol and water is 350% of the weight of the aluminum silver paste; S32, inorganic coating: the above precursor is dropped into tetraethyl orthosilicate within 1 hour and stirred and heated, and the temperature of the whole system is controlled at 60-70 DEG C, under the catalysis of ammonia, the hydrolysis reaction is carried out, after completion, cooling, washing, filtering, inorganic silica coated / graphene coated aluminum silver paste is obtained; tetraethyl orthosilicate is used as the precursor of silicon dioxide, the amount of addition is 40% of the weight of aluminum silver paste; the amount of addition of ammonia is 10% of the weight of aluminum silver paste; S33, organic coating: add toluene to a round bottom flask with stirrer, dropping funnel, reflux condenser, disperse the above inorganic silica coated aluminum silver paste in toluene, the amount of addition of toluene is 350% of the weight of aluminum silver paste; then fully stir for 30 minutes, add silane coupling agent and azobisisobutyronitrile in turn, the amount of addition of silane coupling agent is 2% of the weight of inorganic silica coated aluminum silver paste, the amount of addition of azobisisobutyronitrile is 2% of the weight of inorganic silica coated aluminum silver paste, the system is vacuumed, inert gas is passed, repeated three times, and the whole reaction process is protected in the atmosphere of continuous inert gas, the round bottom flask is placed in a water bath and heated to 70 DEG C, then fluorine-containing acrylic ester monomer is added dropwise, the amount of addition of fluorine-containing acrylic ester monomer is 50% of the weight of inorganic silica coated aluminum silver paste; 1 hour is added dropwise; after the temperature of the system is increased to 85 DEG C, continue to react for 4 hours, cool, wash, filter, organic and inorganic double coated aluminum silver paste is obtained.

2. The graphene-coated aluminum silver powder paint according to claim 1, characterized in that: The epoxy resin is an alicyclic epoxy resin.

3. A method of producing the graphene-coated aluminum silver powder paint according to claim 1 or 2, characterized by, The method comprises the following steps: A component preparation method: (1) add the above dimethylbenzene and n-butanol to a stirring tank, open the high-speed disperser, rotate at a speed of 500-700 r / min for 1-10 min, and obtain a uniform mixed solvent; (2) add the above epoxy resin to the uniform mixed solvent, adjust the rotating speed to 1500-2000 r / min, heat under the condition of 50-100 DEG C, and obtain a mixture A after the alicyclic epoxy resin is completely dissolved; (3) add the above organic and inorganic double coated aluminum silver paste, sericite, aluminum tripolyphosphate and fumed silica to the mixture A, disperse at a speed of 1500-2000 r / min for 2-3 hours, and test the fineness by a doctor blade fineness gauge, wherein the fineness is less than 20 microns, and obtain a mixture B; (4) adjust the rotating speed to 800-1000 r / min, add the above leveling agent and defoaming agent to the mixture B, stir for 10-15 min, filter through a 200-mesh filter cloth, and package; B component preparation method: add the above dimethylbenzene, n-butanol, hexahydrophthalic anhydride and anhydride accelerator to a stirring tank, and stir at a speed of 800-1000 r / min, filter through a 300-mesh filter screen after the hexahydrophthalic anhydride and the anhydride accelerator are completely dissolved, and package.

4. The method according to claim 3, wherein the graphene-coated aluminum silver powder paint is prepared by the following steps: 1) preparing a graphene solution; 2) preparing an aluminum silver powder solution; 3) mixing the graphene solution and the aluminum silver powder solution to obtain a graphene-coated aluminum silver powder paint. The mass ratio of graphene oxide to aluminum silver powder in the graphene oxide dispersion liquid in S12 is 1:500-800.

5. The method for preparing a graphene-coated aluminum silver powder coating according to claim 3, characterized in that: The pH value range in S13 is 1-4.

6. The method of using a graphene-coated aluminum silver powder paint according to claim 1 or 2, characterized in that, The method comprises the following steps: pretreatment: the metal surface is pretreated by sand blasting, degreasing and derusting, washing, phosphating, passivation, deionized water washing, drying of the phosphating film, and elimination of oil stains and dust on the surface of the coated object; Spraying: Mix A component and B component in the ratio of 1:0.5, and spray on the workpiece; Curing: After spraying, let the workpiece dry for 10-20 minutes in a 30℃ environment, and then place the workpiece in a 120-150℃ environment for curing for 1 hour, and polish with 240-mesh sandpaper.

7. The method of using a graphene-coated aluminum silver powder paint according to claim 6, characterized in that: After the curing step, a secondary spraying and curing step is added, Secondary spraying and curing: according to the same spraying and curing steps described above, perform secondary spraying and curing.