CN111534192A

CN111534192A - Anticorrosion and heat dissipation integrated coating of water-based graphene/epoxy zinc-rich dispersion system and preparation method and application thereof

Info

Publication number: CN111534192A
Application number: CN202010318939.8A
Authority: CN
Inventors: 谭正德; 李丰; 吴钧涛; 谢情丽; 赵剩勇
Original assignee: Hunan Kulingster Technology Co ltd
Current assignee: Hunan Kulingster Technology Co ltd
Priority date: 2020-04-21
Filing date: 2020-04-21
Publication date: 2020-08-14
Anticipated expiration: 2040-04-21
Also published as: CN111534192B

Abstract

The invention provides an anticorrosion and heat dissipation integrated coating of a water-based graphene/epoxy zinc-rich dispersion system, and a preparation method and application thereof, and relates to the technical field of water-based coatings. The invention provides an anticorrosion and heat dissipation integrated coating of a water-based graphene/epoxy zinc-rich dispersion system, which comprises the following components in parts by mass: 10-20 parts of water-based epoxy zinc-rich resin, 0.5-1.5 parts of hydrophilic graphene, 0.5-1.5 parts of hydrophilic kaolin, 0.05-0.15 part of fumed silica, 7.2-12.5 parts of water, 1-3 parts of defoaming agent, 0.5-1.5 parts of flatting agent and 1-5 parts of two-component water-based epoxy zinc-rich curing agent. The anticorrosion and heat dissipation integrated coating provided by the invention has excellent anticorrosion performance, can effectively solve the anticorrosion problem of metal materials, is environment-friendly in raw materials, and has low VOC emission.

Description

Anticorrosion and heat dissipation integrated coating of water-based graphene/epoxy zinc-rich dispersion system and preparation method and application thereof

Technical Field

The invention relates to the technical field of water-based paint, in particular to anticorrosion and heat dissipation integrated paint of a water-based graphene/epoxy zinc-rich dispersion system, and a preparation method and application thereof.

Background

The corrosion of metal is mainly caused by that chemical or electrochemical reaction occurs between metal and contact medium, so that the structure of metal is damaged, and the equipment is scrapped. The corrosion of metal causes serious waste of resources and energy, so the problem of corrosion prevention of metal materials is always a key concern of people.

The water-based paint has the advantages of environmental friendliness, small VOC (volatile organic compounds) volatilization and the like, and is widely used for rust prevention of metal products, and the prior rust-preventing water-based paint mainly comprises a water-based polyurethane paint, a water-based polyacrylate paint, a water-based epoxy resin and the like. The waterborne epoxy resin is widely used for preventing corrosion of metal products due to the advantages of no environmental pollution, good operability, strong adhesion to base materials and the like. However, the aqueous epoxy resin has low conductivity and a large amount of hydrophilic groups, so that the corrosion resistance is low. However, the conventional water-based paint sold on the market at present cannot effectively solve the corrosion prevention problem of the metal material.

Disclosure of Invention

In view of the above, the invention aims to provide an anticorrosion and heat dissipation integrated coating of a water-based graphene/epoxy zinc-rich dispersion system, and a preparation method and application thereof. The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system provided by the invention has excellent anticorrosion performance.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides an anticorrosion and heat dissipation integrated coating of a water-based graphene/epoxy zinc-rich dispersion system, which comprises the following components in parts by mass:

10-20 parts of water-based epoxy zinc-rich resin, 0.5-1.5 parts of hydrophilic graphene, 0.5-1.5 parts of hydrophilic kaolin, 0.05-0.15 part of fumed silica, 7.2-12.5 parts of water, 1-3 parts of defoaming agent, 0.5-1.5 parts of flatting agent and 1-5 parts of two-component water-based epoxy zinc-rich curing agent.

Preferably, the hydrophilic graphene is prepared by mixing graphene, an anionic surfactant, a phase transfer catalyst, a dispersant and water and performing a water-borne reaction;

the mass ratio of the graphene to the anionic surfactant to the phase transfer catalyst to the dispersing agent is (1-3): (0.5-1.5): (1-1.5): (1-5).

Preferably, the particle size of the hydrophilic graphene is 0.01-1 μm.

Preferably, the hydrophilic kaolin is prepared by mixing calcined kaolin, an anionic surfactant, a phase transfer catalyst, a dispersant and water and performing a water-borne reaction;

the mass ratio of the calcined kaolin to the anionic surfactant to the phase transfer catalyst to the dispersant is (1-3): (0.5-1.5): (1-1.5): (1-5).

Preferably, the particle size of the hydrophilic kaolin is 0.01-1 μm.

Preferably, the particle size of the fumed silica is 0.01-1 μm.

Preferably, the defoamer comprises one or more of tributyl phosphate, bisamide, fluorinated alkyl phosphate and lauric acid.

Preferably, the leveling agent includes one or more of a UV leveling agent SC-333, a powder leveling agent RB505, a solid leveling agent RB504, and a solid leveling agent RB 503.

The invention also provides a preparation method of the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system, which comprises the following steps:

mixing hydrophilic graphene, hydrophilic kaolin, water and aqueous epoxy zinc-rich resin to obtain doped resin;

and mixing the doped resin with fumed silica, a defoaming agent, a leveling agent and a two-component aqueous epoxy zinc-rich curing agent to obtain the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system.

The invention also provides the application of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system or the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared by the preparation method in the technical scheme in a metal anticorrosion product.

The invention provides an anticorrosion and heat dissipation integrated coating of a water-based graphene/epoxy zinc-rich dispersion system, which comprises the following components in parts by mass: 10-20 parts of water-based epoxy zinc-rich resin, 0.5-1.5 parts of hydrophilic graphene, 0.5-1.5 parts of hydrophilic kaolin, 0.05-0.15 part of fumed silica, 7.2-12.5 parts of water, 1-3 parts of defoaming agent, 0.5-1.5 parts of flatting agent and 1-5 parts of two-component water-based epoxy zinc-rich curing agent. According to the invention, the hydrophilic graphene has ultrahigh heat conductivity coefficient, excellent corrosion resistance and good wear resistance, the surface of the hydrophilic graphene also has hydroxyl, sulfonic group and a small amount of amino hydrophilic groups, the hydrophilic graphene has good hydrophilicity, and the dispersibility in the corrosion-resistant and heat-dissipation integrated coating is high. According to the invention, the hydrophilic kaolin is filled into the aqueous epoxy zinc-rich resin, can be uniformly dispersed in the aqueous epoxy zinc-rich resin, effectively improves the mechanical property and the heat dissipation performance of the anti-corrosion heat dissipation integrated coating of an aqueous graphene/epoxy zinc-rich dispersion system, and obviously improves the mechanical property and the heat conduction and heat dissipation efficiency of the prepared paint film. According to the invention, the water-based zinc-rich epoxy resin has good corrosion resistance, and the corrosion-resistant and heat-dissipation integrated coating prepared by adopting the water-based zinc-rich epoxy resin can improve the corrosion resistance by sacrificing the zinc powder cathode protection in the water-based zinc-rich epoxy resin at the early stage and blocking pores by zinc salt at the later stage, and improving the compactness of a paint film. Therefore, the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system provided by the invention has excellent anticorrosion performance, and can effectively solve the anticorrosion problem of metal materials. The raw materials of the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system provided by the invention are environment-friendly, the production cost is low, and the discharge amount of VOC (volatile organic compounds) of the prepared anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system is low.

Drawings

FIG. 1 is an XRD spectrum of an anticorrosion and heat dissipation integrated coating paint film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1;

FIG. 2 is an FTIR spectrum of an anti-corrosive heat-dissipating integrated coating paint film of the aqueous graphene/epoxy zinc-rich dispersion prepared in example 1;

FIG. 3 is an XPS spectrum of an anti-corrosive heat-dissipating integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1;

FIG. 4 is an XPS spectrum of an anti-corrosive heat-dissipating integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 2;

FIG. 5 is an XPS spectrum of an anti-corrosive heat-dissipating integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 3;

FIG. 6 is an XPS spectrum of a coating paint film prepared in comparative example 1;

fig. 7 is an SEM image of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1;

FIG. 8 is an SEM of the coating made in comparative example 2;

FIG. 9 is a graph of thermal conductivity tests for different coatings.

Detailed Description

In the present invention, the raw materials used are all commercial products which are conventional in the art unless otherwise specified.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises, by mass, 10-20 parts of water-based epoxy zinc-rich resin, preferably 12-18 parts, and more preferably 15 parts. In the invention, the source of the waterborne epoxy zinc-rich resin is preferably HL-W110A-9384 of Shanghaineqing New Material Co. According to the invention, the water-based zinc-rich epoxy resin has good corrosion resistance, and the corrosion-resistant and heat-dissipation integrated coating prepared by adopting the water-based zinc-rich epoxy resin can improve the corrosion resistance by sacrificing the zinc powder cathode protection in the water-based zinc-rich epoxy resin at the early stage and blocking pores by zinc salt at the later stage, and improving the compactness of a paint film.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises, by mass, 0.5-1.5 parts of hydrophilic graphene, preferably 0.8-1.2 parts, and more preferably 1 part of water-based epoxy zinc-rich resin. According to the invention, the hydrophilic graphene has ultrahigh heat conductivity coefficient, excellent corrosion resistance and good wear resistance, the surface of the hydrophilic graphene also has hydroxyl, sulfonic group and a small amount of amino hydrophilic groups, the hydrophilic graphene has good hydrophilicity, and the dispersibility in the corrosion-resistant and heat-dissipation integrated coating is high.

In the invention, the hydrophilic graphene is preferably prepared by mixing graphene, an anionic surfactant, a phase transfer catalyst, a dispersant and water and performing a water-based reaction.

In the invention, the graphene, the anionic surfactant, the phase transfer catalyst, the dispersant and the water are preferably mixed in the order of first mixing the graphene, the anionic surfactant, the phase transfer catalyst and part of water to obtain a graphene mixed solution; secondly, mixing the dispersant and the residual water to obtain a dispersant water solution; and carrying out third mixing on the graphene mixed solution and a dispersant aqueous solution to obtain the hydrophilic graphene. In the present invention, the first mixing mode is preferably magnetic stirring, and the rotation speed and time of the magnetic stirring are not particularly limited in the present invention, and the raw materials may be dissolved. In the present invention, the temperature of the first mixing is preferably 20 to 35 ℃. In the present invention, the second mixing mode is preferably magnetic stirring, and the rotation speed and time of the magnetic stirring are not particularly limited in the present invention, and the raw materials may be dissolved. In the present invention, the temperature of the second mixing is preferably 25 to 27 ℃. In the present invention, the third mixing mode is preferably magnetic stirring; the magnetic stirring time is preferably 1-3 h. The rotation speed of the magnetic stirring is not specially limited, and the raw materials can be uniformly dispersed. In the invention, the mass ratio of the graphene, the anionic surfactant, the phase transfer catalyst and the dispersing agent is preferably (1-3): (0.5-1.5): (1-1.5): (1-5), more preferably 1.5-2.5: 0.8-1.2: 1.2-1.4: 2 to 4. In the present invention, the water is preferably distilled water. In the invention, the volume ratio of the partial water to the residual water is preferably 2-3: 5-9. In the present invention, the particle size of the hydrophilic graphene is preferably 0.01 to 1 μm.

In the present invention, the anionic surfactant preferably includes one or more of sodium lauryl sulfate, sodium lauryl sulfate and lauryl stearic acid. In the preparation process of the hydrophilic graphene, an anionic surfactant is coated on the outer surface of the graphene and is ionized simultaneously to generate a hydrophilic group ether sulfonic group, the ether sulfonic group and an oxygen-containing functional group on the surface of the graphene are subjected to modification reaction to generate a hydroxyl group, a sulfonic group and a small amount of amine groups, the hydrophilicity of the graphene is enhanced, and the hydrophilic graphene is obtained and forms a uniform and stable dispersion system in the anti-corrosion and heat dissipation integrated coating.

In the present invention, the dispersant preferably includes polyvinyl alcohol and/or polyethylene glycol. In the preparation process of the hydrophilic graphene, the dispersant can improve the hydrophilicity of the graphene, so that the dispersibility of the hydrophilic graphene in the anticorrosion and heat dissipation integrated coating is improved.

In the present invention, the phase transfer catalyst preferably comprises one or more of tetrabutylammonium bromide (TBAB), triethylbenzylammonium bromide (TEBA) and cetyltrimethylammonium bromide (CTMAB). In the preparation process of the hydrophilic graphene, the phase transfer catalyst can effectively promote the wetting and dissolving of the graphene in the aqueous solution, and improve the dispersibility of the hydrophilic graphene in the anticorrosion and heat dissipation integrated coating.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises, by mass, 0.5-1.5 parts of hydrophilic kaolin, preferably 0.8-1.2 parts, and more preferably 1 part of water-based epoxy zinc-rich resin. In the invention, the hydrophilic kaolin has excellent mechanical property and heat conduction property, the surface of the hydrophilic kaolin also has hydroxyl, sulfonic group and a small amount of amino hydrophilic groups, the hydrophilic kaolin has good hydrophilicity and high dispersibility in the anticorrosion and heat dissipation integrated coating.

In the present invention, the hydrophilic kaolin is preferably prepared by mixing calcined kaolin, an anionic surfactant, a phase transfer catalyst, a dispersant and water, and performing a hydration reaction.

In the present invention, the calcined kaolin, the anionic surfactant, the phase transfer catalyst, the dispersant and water are preferably mixed in this order by first mixing the calcined kaolin, the anionic surfactant, the phase transfer catalyst and part of the water to obtain a kaolin mixed solution; secondly, mixing the dispersant and the residual water to obtain a dispersant water solution; and thirdly mixing the kaolin mixed solution and a dispersant aqueous solution to obtain the hydrophilic kaolin. In the present invention, the first mixing mode is preferably magnetic stirring, and the rotation speed and time of the magnetic stirring are not particularly limited in the present invention, and the raw materials may be dissolved. In the present invention, the temperature of the first mixing is preferably 20 to 35 ℃. In the present invention, the second mixing mode is preferably magnetic stirring, and the rotation speed and time of the magnetic stirring are not particularly limited in the present invention, and the raw materials may be dissolved. In the present invention, the temperature of the second mixing is preferably 20 to 27 ℃. In the present invention, the third mixing mode is preferably magnetic stirring; the magnetic stirring time is preferably 1-3 h. The rotation speed of the magnetic stirring is not specially limited, and the raw materials can be uniformly dispersed. In the invention, the mass ratio of the calcined kaolin, the anionic surfactant, the phase transfer catalyst and the dispersing agent is preferably (1-3): (0.5-1.5): (1-1.5): (1-5), more preferably 1.5-2.5: 0.8-1.2: 1.2-1.4: 2 to 4. In the present invention, the water is preferably distilled water. In the invention, the volume ratio of the partial water to the residual water is preferably 2-3: 5-9. In the invention, the particle size of the hydrophilic kaolin is preferably 0.01-1 μm. In the invention, the calcination temperature of the calcined kaolin is preferably 400-800 ℃; the calcination time of the calcined kaolin is preferably 4-8 h; the calcined kaolin is preferably prepared by calcining under oxygen conditions. The calcined kaolin has a disordered metakaolin structure, so that part of groups of the inner layer of the original crystal are exposed, the types and the number of surface active points are increased, and the reaction activity is high.

In the present invention, the anionic surfactant preferably includes one or more of sodium lauryl sulfate, sodium lauryl sulfate and lauryl stearic acid. In the preparation process of the hydrophilic kaolin, an anionic surfactant is coated on the outer surface of the kaolin and is ionized simultaneously to generate a hydrophilic group ether sulfonic group, the ether sulfonic group and an oxygen-containing functional group on the surface of the kaolin are subjected to modification reaction to generate a hydroxyl group, a sulfonic group and a small amount of amine hydrophilic groups, the hydrophilicity of the kaolin is enhanced, and the hydrophilic kaolin is obtained and forms a uniform and stable dispersion system in the anticorrosion and heat dissipation integrated coating.

In the present invention, the dispersant preferably includes polyvinyl alcohol and/or polyethylene glycol. In the preparation process of the hydrophilic kaolin, the dispersant can improve the hydrophilicity of the kaolin, so that the dispersibility of the hydrophilic kaolin in the anticorrosion and heat dissipation integrated coating is improved.

In the present invention, the phase transfer catalyst preferably comprises one or more of tetrabutylammonium bromide (TBAB), triethylbenzylammonium bromide (TEBA) and cetyltrimethylammonium bromide (CTMAB). In the preparation process of the hydrophilic kaolin, the phase transfer catalyst can effectively promote the wetting and dissolving of the kaolin in the aqueous solution, and improve the dispersibility of the hydrophilic kaolin in the anticorrosion and heat dissipation integrated coating.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises, by mass, 0.05-0.15 parts of fumed silica, preferably 0.08-0.12 parts of fumed silica, and more preferably 0.1 part of waterborne epoxy zinc-rich resin. In the present invention, the particle size of the fumed silica is preferably 0.01 to 1 μm.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises 1-3 parts by mass of a defoaming agent, preferably 1.2-2.5 parts by mass, and more preferably 2 parts by mass. In the present invention, the antifoaming agent preferably includes one or more of tributyl phosphate, bisamide, fluorinated alkyl phosphate, and lauric acid.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises, by mass, 1-3 parts of a leveling agent, preferably 1.2-2.5 parts, and more preferably 2 parts. In the present invention, the leveling agent includes one or more of a UV leveling agent SC-333, a powder leveling agent RB505, a solid leveling agent RB504, and a solid leveling agent RB 503.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises 1-5 parts of a two-component water-based epoxy zinc-rich curing agent, preferably 2-4 parts, and more preferably 3 parts by mass of a water-based epoxy zinc-rich resin. In the invention, the two-component water-based epoxy zinc-rich curing agent is preferably HL-W110B made by Shanghai Haolii paint Co.

The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system comprises, by mass, 7.2-12.5 parts of water, preferably 9.0-11.0 parts of water, and more preferably 10.0 parts of water; the water is preferably distilled water.

In the invention, the solid content of the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system is preferably 45-55%.

and mixing the doped resin, the fumed silica, the defoaming agent, the leveling agent and the two-component aqueous epoxy zinc-rich curing agent to obtain the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system.

According to the invention, hydrophilic graphene, hydrophilic kaolin, water and aqueous epoxy zinc-rich resin are mixed to obtain the doped resin.

In the present invention, the mixing method is preferably magnetic stirring, and the rotation speed and time of the magnetic stirring are not particularly limited in the present invention, and the raw materials may be uniformly mixed. The mixing sequence of the hydrophilic graphene, the hydrophilic kaolin, the water and the waterborne epoxy zinc-rich resin is not specially limited, and any mixing sequence can be adopted.

After the doped resin is obtained, the doped resin, the fumed silica, the defoaming agent, the leveling agent and the two-component aqueous epoxy zinc-rich curing agent are mixed to obtain the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system.

In the present invention, the mixing method is preferably magnetic stirring, and the rotation speed and time of the magnetic stirring are not particularly limited in the present invention, and the raw materials may be uniformly mixed. The mixing sequence of the doped resin, the fumed silica, the defoaming agent, the flatting agent and the two-component water-based epoxy zinc-rich curing agent is not specially limited, and any mixing sequence can be adopted. The preparation method provided by the invention can ensure that the prepared anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system has excellent performance and does not have the conditions of poor dispersion, flocculation, shrinkage and the like.

The invention also provides an application of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system or the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared by the preparation method in the technical scheme in metal anticorrosion.

The application mode of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system is not particularly limited, and the application mode known to those skilled in the art, such as brushing or coating, can be adopted. In the present invention, the brush amount is preferably 10g/m²(ii) a The coating amount is preferably 10g/m²。

Before brushing or coating the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system, the invention preferably sequentially carries out oil removal, hot water washing, first flow washing, acid washing, second flow washing, surface conditioning, third flow washing, phosphating, recovery, fourth flow washing and drying on the metal surface.

In the present invention, the agent for removing oil is preferably composed of an agent including sodium hydroxide, sodium carbonate and OP emulsifier. In the invention, the mass-volume ratio of the sodium hydroxide, the sodium carbonate and the OP emulsifier is preferably 4-6 g: 10-30 g: 10 to 30mL, more preferably 5 g: 15-25 g: 15-25 mL. In the invention, the temperature for removing the oil is preferably 50-60 ℃; the oil removing time is preferably 1-3 min. In the invention, the metal is preferably soaked in the oil removing agent to remove the oil.

In the present invention, the hot water temperature of the hot water washing is preferably 90 ℃.

In the present invention, the water flow rates of the first, second, third and fourth water washes are independently preferably 1 m/s.

In the present invention, the acid washing reagent is preferably a hydrochloric acid solution having a mass concentration of 10% to 25%. In the invention, the pickling temperature is preferably 40-50 ℃; the pickling time is preferably 0.5-1 min.

In the present invention, the reagent for surface modification is preferably an oxalic acid solution having a mass concentration of 2% to 5%. In the invention, the temperature of the surface adjustment is preferably 20-30 ℃; the time for the surface adjustment is preferably 0.5-1 min. The invention improves the efficiency of subsequent phosphating treatment by surface adjustment, so that fine phosphating crystallization is realized and the phosphating quality is improved.

In the present invention, the phosphating agent is preferably prepared by mixing the following raw materials: zinc nitrate solution, nickel nitrate solution, zinc phosphate solution and tartaric acid solution. In the invention, the mass ratio of zinc nitrate in the zinc nitrate solution, nickel nitrate in the nickel nitrate solution, zinc phosphate in the zinc phosphate solution and tartaric acid in the tartaric acid solution is preferably 80-100: 4-6: 50-60: 0.5 to 1, and more preferably 85 to 95: 5: 55: 0.5. in the invention, the temperature of the phosphorization is preferably 50-53 ℃; the time for phosphorization is preferably 5-15 min. The invention improves the binding force between the metal surface and the coating through phosphating treatment and improves the corrosion resistance.

The following describes the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system, its preparation method and application in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.

Example 1

Weighing 1g of graphene in a beaker, and then weighing 1g of sodium dodecyl sulfate, 0.5g of tetrabutylammonium bromide, 3g of polyvinyl alcohol and 45mL of distilled water for magnetic stirring to obtain hydrophilic graphene;

weighing 2g of calcined kaolin (calcined under the oxygen condition, the calcination temperature is 400 ℃, and the calcination time is 6h) in a beaker, and then weighing 1g of sodium dodecyl sulfate, 0.5g of tetrabutylammonium bromide, 3g of polyvinyl alcohol and 45mL of distilled water for magnetic stirring to obtain hydrophilic kaolin;

weighing 15g of water-based epoxy zinc-rich resin, 1g of hydrophilic graphene, 1g of hydrophilic kaolin and 3ml of water in a beaker, uniformly stirring, weighing 0.1g of fumed silica, adding the fumed silica into the beaker, uniformly stirring, then weighing 2ml of tributyl phosphate, 1ml of a flatting agent and a two-component water-based epoxy zinc-rich curing agent, and stirring for 2 hours by using a DW-2 force-increasing stepless constant-speed stirrer until the materials are uniformly dispersed to obtain the anticorrosion and heat-dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system.

Degreasing (the mass volume ratio of sodium hydroxide, sodium carbonate and OP emulsifier in degreasing agent is 6 g: 30 g: 30mL, the temperature is 60 ℃, the time is 3min), hot water washing (the temperature of hot water is 90 ℃, the flow rate is 1m/s), first washing (the flow rate is 1m/s), acid washing (the acid washing agent is 25% hydrochloric acid solution, the temperature is 50 ℃, the time is 1min), second washing (the flow rate is 1m/s), surface conditioning (the surface conditioning agent is 5% oxalic acid solution, the temperature is 30 ℃, the time is 1min), third washing (the flow rate is 1m/s), phosphating (zinc nitrate in zinc nitrate solution in phosphating agent, nickel nitrate in nickel nitrate solution, phosphorus in zinc phosphate solution) sequentially carried out on the surface of a galvanized steel plate with 12cm × 5cmThe mass ratio of the zinc salt to the tartaric acid in the tartaric acid solution is 100: 6: 60: 1, at the temperature of 50 ℃, for 15min), recovering, washing with fourth stream water (the flow rate is 1m/s) and drying, and then coating the prepared anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system on the surface of a galvanized steel plate, wherein the coating amount is 10g/m²And after curing for 12 hours, obtaining the waterborne epoxy zinc-rich resin coating, and testing the performance of the coating, wherein the test results are shown in Table 3.

The prepared anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system is coated on the surface of a galvanized steel sheet at different temperatures, the drying time of the coating is measured, and the test results are shown in table 4.

Fig. 1 is an XRD spectrum of a paint film of the anticorrosion heat-dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1, and as can be seen from fig. 1, the main components of the coating are an amorphous substance and a part of an inorganic structural substance.

Fig. 2 is an FTIR spectrum of a paint film of the anticorrosion heat-dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1, and as can be seen from fig. 2, organic matters in the coating are mainly epoxy resin.

Example 2

This example differs from example 1 only in that the calcined kaolin employed had a calcination temperature of 600 ℃ and a calcination time of 6 hours.

Example 3

This example differs from example 1 only in that the calcined kaolin employed had a calcination temperature of 800 ℃ and a calcination time of 6 hours.

Example 4

This example differs from example 1 in the amount of starting material used.

Weighing 1g of graphene in a beaker, and then weighing 1g of sodium dodecyl sulfate, 0.5mL of tetrabutylammonium bromide, 3g of polyvinyl alcohol and 45mL of distilled water for magnetic stirring to obtain hydrophilic graphene;

weighing 2g of calcined kaolin in a beaker, and then weighing 1g of sodium dodecyl sulfate, 0.5mL of tetrabutylammonium bromide, 3g of polyvinyl alcohol and 45mL of distilled water for magnetic stirring to obtain hydrophilic kaolin;

weighing 15g of water-based epoxy zinc-rich resin, 0.5g of hydrophilic graphene, 1g of hydrophilic kaolin and 3g of water in a beaker, uniformly stirring, weighing 0.1g of fumed silica, adding the fumed silica into the beaker, uniformly stirring, then weighing 2g of tributyl phosphate, 1g of a flatting agent and 3g of a two-component water-based epoxy zinc-rich curing agent, and stirring for 2h by using a DW-2 force-increasing stepless constant-speed stirrer until the materials are uniformly dispersed to obtain the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system.

The performance of the waterborne epoxy zinc-rich resin coating obtained after coating is tested, and the test results are shown in table 3.

Example 5

This example differs from example 1 in the amount of starting material used.

weighing 15g of water-based epoxy zinc-rich resin, 1.5g of hydrophilic graphene, 1g of hydrophilic kaolin and 3g of water in a beaker, uniformly stirring, weighing 0.1g of fumed silica, adding the fumed silica into the beaker, uniformly stirring, then weighing 2g of tributyl phosphate, 1g of a flatting agent and 3g of a two-component water-based epoxy zinc-rich curing agent, and stirring for 2h by using a DW-2 force-increasing stepless constant-speed stirrer until the materials are uniformly dispersed to obtain the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system.

Comparative example 1

This comparative example differs from example 1 only in that uncalcined kaolin was used as the starting material.

FIG. 3 is an XPS spectrum of an anti-corrosive heat-dissipating integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1; FIG. 4 is an XPS spectrum of an anti-corrosive heat-dissipating integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 2; FIG. 5 is an XPS spectrum of an anti-corrosive heat-dissipating integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 3; FIG. 6 is an XPS spectrum of a coating paint film prepared in comparative example 1. Table 3 shows the contents of elements in kaolin in the raw materials of examples 1 to 3 and comparative example 1. By combining fig. 3-6 and table 1, it can be seen that the inorganic components in the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system are Al and Si.

TABLE 1 elemental contents of Kaolin in examples 1-3 and comparative example 1

Comparative example 2

The present comparative example differs from example 1 only in that graphene is used.

Fig. 7 is an SEM image of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared in example 1; FIG. 8 is an SEM of the coating prepared in comparative example 2. From the analysis of fig. 7 to 8, it can be seen that the surface of the anti-corrosion and heat-dissipation integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system prepared by the invention is uniform and fine, and the hydrophilic graphene and the hydrophilic kaolin are uniformly embedded in the anti-corrosion and heat-dissipation integrated coating film of the aqueous graphene/epoxy zinc-rich dispersion system.

Heat dissipation performance test

Comparative example 3

The Taiwan product (IC200 oil-based ink, Shenzhen high-tech coating Co., Ltd.) was weighed 10g, diluted with 5g of ethyl acetate to a consistency of 3 grade (four cup painting), stirred uniformly to obtain a coating, which was recorded as control (baseline), and coated on the surface of a glass plate of 10cm × 5 cm. The heat dissipation performance of the paint was tested, and the test results are shown in fig. 9.

Comparative example 4

Weighing 15g of waterborne epoxy zinc-rich resin, 1g of waterborne kaolin prepared in example 1 and 1g of distilled water in a beaker, uniformly stirring, weighing 0.1g of fumed silica, adding the fumed silica into the beaker, uniformly stirring, then weighing 2g of tributyl phosphate, 1g of a leveling agent and 3g of a two-component waterborne epoxy zinc-rich curing agent, stirring for 4 hours by using a DW-2 force-increasing stepless constant-speed stirrer until the waterborne epoxy zinc-rich curing agent is uniformly dispersed to obtain a coating, which is marked as NO.1, and coating the coating on the surface of a 10cm × 5cm glass plate. The heat dissipation performance of the paint was tested, and the test results are shown in fig. 9.

Comparative example 5

Weighing 15g of waterborne epoxy zinc-rich resin, 1g of waterborne graphene prepared in example 1 and 3g of distilled water, uniformly stirring the materials in a beaker, weighing 0.1g of fumed silica, adding the fumed silica into the beaker, uniformly stirring the materials, then weighing 2g of tributyl phosphate, 1g of a flatting agent and 3g of a two-component waterborne epoxy zinc-rich curing agent, stirring the materials for 4 hours by using a DW-2 force-increasing stepless constant-speed stirrer until the materials are uniformly dispersed to obtain a coating, marking as NO.3, and coating the coating on the surface of a 10cm × 5cm glass plate. The heat dissipation performance of the paint was tested, and the test results are shown in fig. 9.

The anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared in the example 1 is marked as NO.3, and is coated on the surface of a glass plate with the thickness of 10cm multiplied by 5 cm. The heat dissipation performance of the anticorrosion heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system is tested, and the test result is shown in fig. 9.

Comparative example 6

Weighing 1g of carbon nano tube in a beaker, then weighing 2g of sodium dodecyl sulfate, 0.5g of tetrabutylammonium bromide, 3g of polyvinyl alcohol and 45mL of distilled water, and carrying out magnetic stirring to obtain a carbon nano tube dispersion liquid;

weighing 15g of water-based epoxy resin, 8g of carbon nanotube dispersion liquid, 12g of kaolin prepared in example 1 and 3g of distilled water in a beaker, uniformly stirring by using a glass rod, then weighing 1g of tributyl phosphate 1g of flatting agent and 3g of two-component water-based epoxy zinc-rich curing agent, stirring for 3 hours by using a DW-2 force-increasing stepless constant-speed stirrer until the leveling agent and the two-component water-based epoxy zinc-rich curing agent are uniformly dispersed to obtain a coating, marking as NO.4, and coating the coating on the surface of a 10cm × 5cm glass plate. The heat dissipation performance of the paint was tested, and the test results are shown in fig. 9.

Comparative example 7

Weighing 15g of water-based epoxy resin, 10g of carbon nano tube dispersion liquid prepared in comparative example 4, 12g of kaolin prepared in example 1 and 3g of distilled water in a beaker, uniformly stirring by using a glass rod, then weighing 1g of tributyl phosphate, 1g of flatting agent and 3g of two-component water-based epoxy zinc-rich curing agent, stirring for 3 hours by using a DW-2 force-increasing stepless constant-speed stirrer until the leveling agent and the two-component water-based epoxy zinc-rich curing agent are uniformly dispersed to obtain a coating, marking as NO.5, and coating the coating on the surface of a 10cm multiplied by. The heat dissipation performance of the paint was tested, and the test results are shown in fig. 9.

Comparative example 8

Weighing 15g of water-based epoxy resin, 12g of carbon nano tube dispersion liquid prepared in comparative example 4, 12g of kaolin prepared in example 1 and 3g of distilled water in a beaker, uniformly stirring by using a glass rod, then weighing 1g of tributyl phosphate, 1g of flatting agent and 3g of two-component water-based epoxy zinc-rich curing agent, stirring for 3 hours by using a DW-2 force-increasing stepless constant-speed stirrer until the leveling agent and the two-component water-based epoxy zinc-rich curing agent are uniformly dispersed to obtain a coating, marking as NO.6, and coating the coating on the surface of a 10cm multiplied by. The heat dissipation performance of the paint was tested, and the test results are shown in fig. 9.

Fig. 9 is a heat conductivity test chart of different coatings, and it can be seen from fig. 9 that the anti-corrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared by the present invention has good heat dissipation performance, and the maximum temperature difference between the inside and the outside is 13 ℃.

Comparative example 9

This comparative example differs from example 1 in the amount of starting material used.

weighing 15g of water-based epoxy zinc-rich resin, 2g of hydrophilic graphene, 1g of hydrophilic kaolin and 3g of water in a beaker, uniformly stirring, weighing 0.1g of fumed silica, adding the fumed silica into the beaker, uniformly stirring, then weighing 2g of tributyl phosphate, 1g of a flatting agent and 3g of a two-component water-based epoxy zinc-rich curing agent, and stirring for 2h by using a DW-2 force-increasing stepless constant-speed stirrer until the materials are uniformly dispersed to obtain the coating.

The properties of the coatings obtained after coating were tested and the results are shown in table 3.

The prepared coating is coated on the surface of a galvanized steel sheet at different temperatures, the drying time of the coating is measured, and the test results are shown in table 4.

TABLE 3 results of the Performance test of the coatings obtained in examples 1, 4 to 5 and comparative example 3

According to the analysis of the experimental results, the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system has better paint film performance than the conventional similar oily system products in the prior art.

TABLE 4 drying time of the coatings obtained in examples 1, 4 to 5 and comparative example 3

According to the analysis of the test results, the hydrophilic graphene and the hydrophilic kaolin are added into the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system, so that the anticorrosion performance and the heat dissipation performance of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system can be remarkably improved, and the coating can be quickly dried.

Analysis by combining tables 3 and 4 shows that the raw materials of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared by the invention are more environment-friendly, lower in production cost and less in VOC (volatile organic compounds) emission compared with the raw materials of the conventional similar oily system products in the prior art.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. An anticorrosion and heat dissipation integrated coating of a water-based graphene/epoxy zinc-rich dispersion system is characterized by comprising the following components in parts by mass:

2. The anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system according to claim 1, wherein the hydrophilic graphene is prepared by mixing raw materials including graphene, an anionic surfactant, a phase transfer catalyst, a dispersant and water and performing a water-borne reaction;

3. The anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system according to claim 1 or 2, wherein the particle size of the hydrophilic graphene is 0.01-1 μm.

4. The anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system according to claim 1, wherein the hydrophilic kaolin is prepared by mixing calcined kaolin, an anionic surfactant, a phase transfer catalyst, a dispersant and water and performing a water-borne reaction;

5. The anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system according to claim 1 or 4, wherein the particle size of the hydrophilic kaolin is 0.01-1 μm.

6. The anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system according to claim 1, wherein the particle size of the fumed silica is 0.01-1 μm.

7. The aqueous graphene/epoxy zinc-rich dispersion anticorrosion and heat dissipation integrated coating of claim 1, wherein the defoamer comprises one or more of tributyl phosphate, bisamide, fluorinated alkyl phosphate and lauric acid.

8. The anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system according to claim 1, wherein the leveling agent comprises one or more of a UV leveling agent SC-333, a powder leveling agent RB505, a solid leveling agent RB504 and a solid leveling agent RB 503.

9. The preparation method of the anticorrosion and heat dissipation integrated coating of the water-based graphene/epoxy zinc-rich dispersion system of any one of claims 1 to 8 is characterized by comprising the following steps:

10. The application of the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system according to any one of claims 1 to 8 or the anticorrosion and heat dissipation integrated coating of the aqueous graphene/epoxy zinc-rich dispersion system prepared by the preparation method according to claim 9 in metal anticorrosion products.