Graphene waterborne anticorrosive material, graphene waterborne anticorrosive coating, graphene waterborne anticorrosive paint, and preparation method and application thereof

Abstract

This invention relates to the field of corrosion protection technology, specifically to a graphene-based waterborne anti-corrosion material, a graphene-based waterborne anti-corrosion coating, a graphene-based waterborne anti-corrosion paint, and their preparation methods and applications. The graphene-based waterborne anti-corrosion material includes a graphene-based waterborne anti-corrosion coating, comprising, by weight: 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drying agent, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, and 10-50 parts filler; the modified graphene includes graphene oxide and phytate grafted onto the surface of graphene oxide via amide bonds. The graphene-based waterborne anti-corrosion paint of this invention can dry and cure rapidly, significantly improving the ease of application. Furthermore, the coating prepared by the paint exhibits significantly improved durability under long-term immersion in liquid, and the graphene in the coating possesses dispersion stability and excellent resistance to salt spray corrosion.

Description

Technical Field

[0001] This invention relates to corrosion protection technology, specifically to a graphene waterborne anti-corrosion material, a graphene waterborne anti-corrosion coating, a graphene waterborne anti-corrosion paint, and their preparation methods and applications. Background Technology

[0002] Metal corrosion poses serious safety hazards and causes enormous economic losses, as well as severe environmental pollution. Driven by the concepts of energy conservation, emission reduction, and low-carbon environmental protection, water-based coatings, with their advantages of low VOC content, good substrate wettability, and excellent decorative effects, reduce harm to the environment and construction workers during coating production, transportation, application, and use. They also offer the advantage of low cost. Therefore, water-based coatings are gradually replacing traditional solvent-based coatings in areas requiring corrosion protection of metal substrates. However, currently available products suffer from problems such as slow drying, poor water resistance, and poor salt spray corrosion resistance.

[0003] CN118652619A discloses an organosilicon-modified waterborne polyurethane coating, which uses diisocyanate-modified graphene oxide as a curing agent additive to improve the agglomeration of graphene oxide in waterborne polyurethane and enhance the water resistance and abrasion resistance of the coating film. However, the above system is a waterborne polyurethane system, which has problems with low hardness and poor salt spray resistance, posing challenges for its application in the petrochemical industry.

[0004] CN103756548A discloses a water-based high-solids coating and its preparation method. The coating formula increases the solids content by adding a large amount of powder. At the same time, it uses an emulsion with a high glass transition temperature and a low film-forming temperature as the film-forming substance, which ensures the fast drying of the paint film. However, this results in harsh conditions for coating application and makes it difficult to be universally applicable. CN113913113A discloses a method for preparing water-based ultra-fast drying anti-corrosion coatings. This method involves reacting amino-terminated dimethyl silicone oil with graphene oxide to obtain modified graphene / organosilicon oil, which is then used to prepare a water-based ultra-fast drying anti-corrosion coating for oil pipelines. However, due to the inherent properties of the graphene oxide used, the overall effect did not meet expectations.

[0005] Therefore, it is of great significance to develop a graphene waterborne anti-corrosion coating that combines the technical characteristics of rapid drying, excellent water resistance, good salt spray corrosion resistance, and high adhesion. Summary of the Invention

[0006] To overcome the problems of poor water resistance, poor salt spray corrosion resistance, slow drying speed, and poor adhesion of existing water-based anti-corrosion coatings, this invention provides a graphene water-based anti-corrosion material, a graphene water-based anti-corrosion coating, a graphene water-based anti-corrosion coating, its preparation method, and its application. The graphene water-based anti-corrosion coating of this invention has the advantage of rapid drying (<30 min), and the coating formed by the graphene water-based anti-corrosion coating of this invention has the advantages of excellent water resistance, good salt spray corrosion resistance, and high adhesion.

[0007] To achieve the above objectives, the first aspect of the present invention provides a graphene-based waterborne anti-corrosion material, which includes a graphene-based waterborne anti-corrosion coating. The graphene-based waterborne anti-corrosion coating comprises, by weight, 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drying agent, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, and 10-50 parts filler. The modified graphene comprises graphene oxide and ammonium phytate grafted onto the surface of graphene oxide via amide bonds, the structure of which is shown in formula (I). (I), In formula (I), * represents the N-linked site in the amide bond; R1 is selected from one of the groups formed by removing two terminal amino groups from C2-C10 alkylene or n-ethylene(n+1)amines, where n is an integer and 2≤n≤6.

[0008] A second aspect of the present invention provides a graphene-based waterborne anti-corrosion coating, the coating comprising: By weight, the composition includes 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drying agent, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, 10-50 parts filler, and 20-55 parts deionized water. The modified graphene comprises graphene oxide and ammonium phytate grafted onto the surface of graphene oxide via amide bonds, the structure of which is shown in formula (I). (I), In formula (I), * represents the N-linked site in the amide bond; R1 is selected from one of the groups formed by removing two terminal amino groups from C2-C10 alkylene or n-ethylene(n+1)amines, where n is an integer and 2≤n≤6.

[0009] A third aspect of the present invention provides a method for preparing the graphene waterborne anti-corrosion coating of the present invention, the method comprising: mixing the components of the coating.

[0010] A fourth aspect of the present invention provides a graphene-based waterborne anti-corrosion coating, which is prepared from the graphene-based waterborne anti-corrosion coating described in the present invention.

[0011] The fifth aspect of this invention provides an application of the graphene waterborne anti-corrosion material, graphene waterborne anti-corrosion coating, or graphene waterborne anti-corrosion coating described herein in the petroleum, chemical, power, and electronics industries.

[0012] Through the above technical solution, the graphene waterborne anti-corrosion coating of the present invention can be dried and cured quickly, which significantly improves the convenience of construction. Moreover, the durability of the coating prepared by the coating under long-term immersion in liquid is significantly improved. On the other hand, the graphene in the coating has dispersion stability and excellent salt spray corrosion resistance, avoiding the problems of demulsification and sedimentation of traditional waterborne coatings during long-term storage.

[0013] Meanwhile, the components of the graphene-based waterborne anti-corrosion coating described in this invention work synergistically, enabling rapid drying while ensuring the coating's water resistance, salt spray corrosion resistance, and high adhesion, achieving zero addition of traditional anti-corrosion fillers such as zinc and aluminum. Furthermore, the introduction of modified graphene into the graphene-based waterborne anti-corrosion coating of this invention facilitates the uniform dispersion of graphene in the coating, solves the problem of graphene self-agglomeration, and allows graphene to expand into a sheet-like structure in the waterborne anti-corrosion coating, providing excellent molecular barrier properties, extending the diffusion path of corrosive agents, and solving the technical problems of cracking, blistering, adhesion degradation, and poor corrosion resistance in traditional waterborne coatings after long-term immersion in water. Attached Figure Description

[0014] Figure 1 The infrared spectra of graphene oxide, amidated modified graphene, and modified graphene prepared in Example 1 of this invention are shown. Figure 2 The X-ray photoelectron spectroscopy of the modified graphene prepared in Example 1 of this invention is shown. Figure 3 The N1s X-ray photoelectron spectrum of the modified graphene prepared in Example 1 of this invention is shown. Figure 4 This is the P2p X-ray photoelectron spectrum of the modified graphene prepared in Example 1 of this invention. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] The first aspect of this invention provides a graphene-based waterborne anti-corrosion material, which includes a graphene-based waterborne anti-corrosion coating. The graphene-based waterborne anti-corrosion coating comprises, by weight, 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drying agent, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, and 10-50 parts filler. The modified graphene comprises graphene oxide and ammonium phytate grafted onto the surface of graphene oxide via amide bonds, the structure of which is shown in formula (I). (I), In formula (I), * represents the N-linked site in the amide bond; R1 is selected from one of the groups formed by removing two terminal amine groups from a C2-C10 alkylene group or an n-ethylene(n+1)amine, where n is an integer and 2≤n≤6. The graphene waterborne anti-corrosion material of the present invention has the advantages of excellent water resistance and good salt spray corrosion resistance.

[0017] In this invention, the group formed by removing two terminal amino groups from n-ethylene (n+1) amines, for example, triethylenetetramine becomes -CH2CH2NHCH2CH2NHCH2CH2- after removing two terminal amino groups. Other n-ethylene (n+1) amines (such as tetraethylenepentamine, diethylenetriamine, etc.) formed by removing two terminal amino groups are not listed here.

[0018] According to a preferred embodiment of the present invention, R1 is selected from one of the groups formed by removing two terminal amino groups from a C2-C6 alkylene group or an n-ethylene (n+1)amine, wherein n is an integer and 2≤n≤5. Preferably, R1 is selected from one of ethylene, hexane, -CH2CH2NHCH2CH2-, -CH2CH2NHCH2CH2NHCH2CH2-, and -CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-.

[0019] In this art, the structural formula of graphene oxide is generally considered to be as shown in formula (II). (II).

[0020] In this invention, the ammonium phytate salt in the modified graphene can be grafted onto the surface of graphene oxide via amide bonds. Depending on the number of carboxyl groups on the graphene oxide surface, for example, one, two, three, four, five, six, seven, or eight of the ammonium phytate salts described in this invention can be grafted. Hereinafter, an exemplary structural formula of modified graphene grafted with one ethylene phytate salt (R1) is given, as shown in formula (III). (III) The structural formulas of the remaining phytate ammonium salts of the R1 group and the modified graphene structures grafted with 1, 2, 3, 4, 5, 6, 7 or 8 phytate ammonium salts will not be described in detail.

[0021] In this invention, the modified graphene within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the modified graphene is 1-3 parts by weight.

[0022] In this invention, all epoxy resins within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the epoxy resin is 10-30 parts by weight.

[0023] In this invention, all cobalt-free drying agents within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the cobalt-free drying agent is 0.01-0.1 parts by weight.

[0024] In this invention, all fillers within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the filler is 15-40 parts by weight.

[0025] In this invention, the adhesion of the graphene water-based anti-corrosion coating has a wide range of selectable values, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the adhesion of the coating is ≥3MPa, preferably 4-6MPa.

[0026] In this invention, the thickness of the graphene water-based anti-corrosion coating can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the thickness is 30μm-80μm.

[0027] According to a preferred embodiment of the present invention, the graphene water-based anti-corrosion coating does not contain zinc or cobalt.

[0028] In this invention, the carbon content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the carbon content of the phenol-modified graphene is 35wt%-60wt% by mass.

[0029] In this invention, the nitrogen content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the nitrogen content of the modified graphene is 1wt%-5wt% by mass.

[0030] In this invention, the phosphorus content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the phosphorus content of the modified graphene is 1wt%-5wt% by mass.

[0031] In this invention, the oxygen content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the oxygen content of the modified graphene is 10wt%-35wt% by mass.

[0032] In this invention, the particle size of the modified graphene can be selected within a wide range. According to a preferred embodiment of this invention, the median particle size of the modified graphene is 5μm-15μm, for example, 6μm, 8μm, 10μm, 12μm, or 14μm. In this invention, by adding modified graphene, the problem of graphene self-aggregation is solved, which is beneficial to the uniform dispersion of graphene in the coating. This allows the graphene to spread into a sheet-like structure in the water-based anti-corrosion coating, providing excellent molecular barrier properties, extending the diffusion path of corrosive agents, and solving the technical problems of cracking, blistering, adhesion degradation, and poor corrosion resistance of traditional water-based coatings after long-term immersion in water. This significantly improves the durability of the coating under long-term immersion in liquid.

[0033] In this invention, the modified graphene includes an organic amine grafted onto the surface of graphene oxide via an amide bond, and phytic acid forming an ammonium phytate salt with the terminal amine group of the organic amine. The organic amine is selected from one or more of organic diamines and organic polyamines. According to a preferred embodiment of this invention, the organic amine is selected from one or more of triethylenetetramine, hexamethylenediamine, ethylenediamine, tetraethylenepentamine, and diethylenetriamine. The organic amine undergoes an amidation reaction with the carboxyl groups on the surface of graphene oxide under the action of a catalyst to obtain amidated modified graphene. The modified graphene material is further obtained by combining phytic acid with the amine group at the amide terminal group to form an ammonium phytate salt. According to one embodiment of this invention, this invention provides a method for preparing the modified graphene, comprising: (1) reacting an organic amine with graphene oxide in the presence of a first solvent and an amidation catalyst to separate amidated graphene. (2) In the presence of a second solvent, phytic acid is contacted with amide graphene, separated, and the solid is dried; the organic amine is selected from one or more of C2-C10 organic diamines and C2-C6 organic polyamines.

[0034] According to a preferred embodiment of the present invention, the amidation catalyst is selected from one or more of methyl orthosilicate, diphenylsilane, carbodiimide, urea cationic / quaternary phosphine salt, benzotriazole, borane, and hydrocarbon-substituted borane. The mass ratio of the amidation catalyst to graphene oxide is 0.01-0.05:1.

[0035] According to a preferred embodiment of the present invention, the organic amine is selected from one or more of triethylenetetramine, hexamethylenediamine, ethylenediamine, tetraethylenepentamine, and diethylenetriamine.

[0036] According to a preferred embodiment of the present invention, the mass ratio of organic amine to graphene oxide is 0.02-0.1:1.

[0037] According to a preferred embodiment of the present invention, the mass ratio of phytic acid to aminated graphene is 0.1-0.7:1.

[0038] In this invention, the range of amidation conditions is relatively wide. According to a preferred embodiment of this invention, the amidation conditions include: a temperature of 60-150°C and a time of 30-120 min.

[0039] According to a preferred embodiment of the present invention, the first solvent is N,N-dimethylformamide and the second solvent is water.

[0040] In this invention, the range of selectable contact conditions is relatively wide. According to a preferred embodiment of this invention, the amidation conditions include: a temperature of 60-100°C and a time of 3-8 hours.

[0041] According to a preferred embodiment of the present invention, the cobalt-free drying agent contains vanadium, which can improve the rapid drying and curing speed of the coating.

[0042] In this invention, the vanadium content in the cobalt-free drying agent can be selected from a wide range, which is an illustrative example, but does not limit the scope of the invention. According to a preferred embodiment of the invention, the vanadium content in the cobalt-free drying agent is not less than 2.5 wt%, preferably 3-7 wt%.

[0043] According to a preferred embodiment of the present invention, the cobalt-free drying agent is vanadium isooctanoate.

[0044] In this invention, the range of epoxy resins that can be selected is relatively wide. According to a preferred embodiment of this invention, the epoxy resin is selected from one or more of acrylic resins, alkyd resins and polyurethane resins, preferably alkyd resins. The selection of the aforementioned resins can improve the dispersion stability of graphene in the coating and the stability of the coating.

[0045] In this invention, the range of alkanolamines that can be selected is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the alkanolamines are selected from one or more of 2-amino-2-methyl-1-propanol, ethanolamine, and butanolamine.

[0046] In this invention, the viscosity of the polyurethane thickener can be selected over a wide range. According to a preferred embodiment of this invention, the viscosity of the polyurethane thickener at 25°C is 1000-10000 mPa•s, for example, 1500 mPa•s, 2000 mPa•s, 3000 mPa•s, 4000 mPa•s, 5000 mPa•s, 6000 mPa•s, 7000 mPa•s, 8000 mPa•s, 9000 mPa•s. The synergistic effect of the polyurethane thickener with viscosity in the aforementioned range, along with alkanolamines and organosilicon dispersants, improves the dispersibility and stability of graphene and fillers in the coating, resulting in a coating with high viscosity and good wetting effect while maintaining good fluidity and wettability.

[0047] In this invention, a wide range of silicone dispersants can be selected. According to a preferred embodiment of the invention, the silicone dispersant is a polyether siloxane copolymer dispersant. The synergistic effect of the aforementioned silicone dispersants with alkanolamines and polyurethane thickeners improves the dispersion stability of graphene and inorganic fillers in the coating and the stability of the coating itself, resulting in high viscosity and good wetting effect while maintaining good flowability and wettability. According to a preferred embodiment of the invention, the silicone dispersant is selected from one or more of Tego-100, Tego-260, Tego-270, Tego-280, Tego-410, and Tego-800.

[0048] In this invention, the range of filler types is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the inorganic filler is selected from one or more of aluminum tripolyphosphate, barium sulfate, titanium dioxide, carbon black, calcium carbonate, flake glass, bentonite, talc, zinc oxide, mica powder, and mica iron oxide.

[0049] A second aspect of the present invention provides a graphene-based waterborne anti-corrosion coating, the coating comprising: By weight, the composition includes 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drying agent, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, 10-50 parts filler, and 20-55 parts deionized water. The modified graphene comprises graphene oxide and phytate grafted onto the surface of graphene oxide via amide bonds, the structural formula of which is shown in formula (I). (I), In formula (I), * represents the N-linked site in the amide bond; R1 is selected from one of the groups formed by removing two terminal amine groups from a C2-C10 alkylene group or an n-ethylene(n+1)amine, where n is an integer and 2≤n≤6. The graphene waterborne anti-corrosion material described in this invention has the advantages of rapid drying (<30min), excellent water resistance, good salt spray corrosion resistance, and high adhesion.

[0050] According to a preferred embodiment of the present invention, R1 is selected from one of ethylene, hexane, -CH2CH2NHCH2CH2-, -CH2CH2NHCH2CH2NHCH2CH2-, and -CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-.

[0051] In this invention, the modified graphene within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the modified graphene is 1-3 parts by weight.

[0052] In this invention, all epoxy resins within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the epoxy resin is 10-30 parts by weight.

[0053] In this invention, all cobalt-free drying agents within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the cobalt-free drying agent is 0.01-0.1 parts by weight.

[0054] In this invention, all fillers within the aforementioned range can achieve the purpose of this invention. According to a preferred embodiment of this invention, the filler is 15-40 parts by weight.

[0055] In this invention, the carbon content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the carbon content of the phenol-modified graphene is 35wt%-60wt% by mass.

[0056] In this invention, the nitrogen content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the nitrogen content of the modified graphene is 1wt%-5wt% by mass.

[0057] In this invention, the phosphorus content in the modified graphene can be selected from a wide range, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the phosphorus content of the modified graphene is 1wt%-5wt% by mass.

[0058] In this invention, the particle size of the modified graphene can be selected within a wide range. According to a preferred embodiment of this invention, the median particle size of the modified graphene is 5μm-15μm, for example, 6μm, 8μm, 10μm, 12μm, or 14μm. In this invention, by adding modified graphene, the problem of graphene self-aggregation is solved, which is beneficial to the uniform dispersion of graphene in the coating. This allows the graphene to spread into a sheet-like structure in the water-based anti-corrosion coating, providing excellent molecular barrier properties, extending the diffusion path of corrosive agents, and solving the technical problems of cracking, blistering, adhesion degradation, and poor corrosion resistance of traditional water-based coatings after long-term immersion in water. This significantly improves the durability of the coating under long-term immersion in liquid.

[0059] In this invention, the types of modified graphene, epoxy resin, cobalt-free drying agent, alkanolamine, organosilicon dispersant, polyurethane thickener, and filler have been described in detail above. The following is an illustrative description, but the scope remains similar to that described above.

[0060] According to a preferred embodiment of the present invention, the cobalt-free drying agent contains vanadium, which can improve the rapid drying and curing speed of the coating.

[0061] In this invention, the vanadium content in the cobalt-free drying agent can be selected from a wide range, which is an illustrative example, but does not limit the scope of the invention. According to a preferred embodiment of the invention, the vanadium content in the cobalt-free drying agent is not less than 2.5 wt%, preferably 3-7 wt%.

[0062] According to a preferred embodiment of the present invention, the cobalt-free drying agent is vanadium isooctanoate.

[0063] In this invention, the range of epoxy resins that can be selected is relatively wide. According to a preferred embodiment of this invention, the epoxy resin is selected from one or more of acrylic resins, alkyd resins and polyurethane resins, preferably alkyd resins. The selection of the aforementioned resins can improve the dispersion stability of graphene in the coating and the stability of the coating.

[0064] In this invention, the range of alkanolamines that can be selected is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the alkanolamines are selected from one or more of 2-amino-2-methyl-1-propanol, ethanolamine, and butanolamine.

[0065] In this invention, the viscosity of the polyurethane thickener can be selected over a wide range. According to a preferred embodiment of this invention, the viscosity of the polyurethane thickener at 25°C is 1000-10000 mPa•s, for example, 1500 mPa•s, 2000 mPa•s, 3000 mPa•s, 4000 mPa•s, 5000 mPa•s, 6000 mPa•s, 7000 mPa•s, 8000 mPa•s, 9000 mPa•s. The synergistic effect of the polyurethane thickener with viscosity in the aforementioned range, along with alkanolamines and organosilicon dispersants, improves the dispersibility and stability of graphene and fillers in the coating, resulting in a coating with high viscosity and good wetting effect while maintaining good fluidity and wettability.

[0066] In this invention, the range of types of organosilicon dispersants is relatively wide. According to a preferred embodiment of this invention, the organosilicon dispersant is a polyether siloxane copolymer dispersant. The synergistic effect of the aforementioned organosilicon dispersants with alkanolamines and polyurethane thickeners improves the dispersion stability of graphene and inorganic fillers in the coating and the stability of the coating, so that the coating has high viscosity and good wetting effect while maintaining good fluidity and wettability.

[0067] In this invention, a wide range of polyether siloxane copolymer dispersants can be selected, which is illustrative but does not limit the scope of the invention. According to a preferred embodiment of the invention, the organosilicon dispersant is selected from one or more of Tego-100, Tego-260, Tego-270, Tego-280, Tego-410 and Tego-800.

[0068] In this invention, the range of filler types is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the inorganic filler is selected from one or more of aluminum tripolyphosphate, barium sulfate, titanium dioxide, carbon black, calcium carbonate, flake glass, bentonite, talc, zinc oxide, mica powder, and mica iron oxide.

[0069] In this invention, the filler is selected from filler 1 and filler 2. According to a preferred embodiment of the invention, filler 1 is selected from one or more of aluminum tripolyphosphate, titanium dioxide, mica powder, mica iron oxide, calcium carbonate and flake glass; filler 2 is selected from one or more of bentonite, talc, zinc oxide, barium sulfate and carbon black.

[0070] In this invention, the content of filler 1 and filler 2 in the total weight of filler can be selected within a wide range. According to a preferred embodiment of this invention, filler 1 accounts for 40-80 wt% of the total weight of filler, and filler 2 accounts for 20-60 wt% of the total weight of filler.

[0071] In this invention, the solid content in the graphene waterborne anti-corrosion coating can be selected from a wide range. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solid mass fraction of the coating is 45wt%-65wt%.

[0072] This invention does not impose special requirements on the preparation method of the coating; conventional mixing is sufficient. A third aspect provides a method for preparing the graphene-based waterborne anti-corrosion coating described in this invention, the method comprising: mixing the components of the coating. The waterborne anti-corrosion coating prepared by the method of this invention has the advantages of rapid drying (<30 min), excellent water resistance, good salt spray corrosion resistance, and high adhesion.

[0073] According to a preferred embodiment of the present invention, the preparation method of the graphene waterborne anti-corrosion coating includes: (1) Mix modified graphene, epoxy resin, alkanolamine, polyurethane thickener, filler 1 and deionized water and perform first shearing and first grinding; (2) The product from step (1) is mixed with filler 2, cobalt-free drying agent, organosilicon dispersant and deionized water, followed by a second shearing and a second grinding. The aforementioned preferred preparation method can improve water resistance.

[0074] In this invention, the first shearing condition is not particularly limited; conventional shearing conditions in the art are sufficient. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the first shearing condition includes: a rotation speed of 1200 rpm to 1500 rpm; a temperature of 30 to 50°C; and a time that can be determined according to the actual situation, generally 10 to 60 minutes.

[0075] In this invention, the first grinding conditions are not particularly limited, and conventional grinding conditions in the art are sufficient. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the first grinding conditions include: grinding to a fineness ≤25μm, for example, a sand mill can be used for the grinding. Preferably, the grinding media of the sand mill is 0.8mm-1.0mm zirconium beads; the rotation speed is 400-600rpm; and the time can be determined according to the actual situation, generally 30-60min.

[0076] In this invention, the second shearing condition is not particularly limited; conventional shearing conditions in the art are sufficient. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the second shearing condition includes: a rotational speed of 800 rpm to 1500 rpm; and a time that can be determined according to the actual situation, generally 10 to 60 minutes.

[0077] In this invention, the second grinding conditions are not particularly limited; conventional grinding conditions in the art are sufficient. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the second grinding conditions include: grinding to a fineness ≤30μm, for example, a sand mill can be used for the grinding. Preferably, the grinding media of the sand mill is 0.8mm-1.5mm zirconium beads; the rotation speed is 400-600rpm; and the time can be determined according to the actual situation, generally 15-30min.

[0078] A fourth aspect of this invention provides a graphene-based waterborne anti-corrosion coating, which is prepared from the graphene-based waterborne anti-corrosion coating described in this invention. The graphene-based waterborne anti-corrosion coating described in this invention exhibits excellent water resistance, good salt spray corrosion resistance, and high adhesion.

[0079] The fifth aspect of this invention provides an application of the graphene waterborne anti-corrosion material, graphene waterborne anti-corrosion coating and graphene waterborne anti-corrosion coating described in this invention in the petroleum, chemical, power and electronics industries.

[0080] In the context and embodiments of this invention, the basic performance of the water-based anti-corrosion coating is tested according to HG / T4847-2015, the water resistance test is conducted according to GB / T 1733-1993, the salt spray resistance test is conducted according to GB / T1771-2007, the film adhesion test is conducted according to GB / T 5210-2006, and the film is cleaned before coating according to GB / T8923.1-2011.

[0081] In the context of this invention specification, including the following embodiments, the content of each element was obtained by X-ray photoelectron spectroscopy (XPS) using an ESCALAB 250Xi XPS instrument from Thermo Fisher Scientific, USA. Test conditions: room temperature 25°C, vacuum degree less than 5 × 10⁻⁶. -10 The mba operates at 15KV and uses Al Kα as the radiation source.

[0082] The morphology of the material was characterized using a scanning electron microscope (SEM) in the following embodiments, as described in this specification. Specifically, the scanning electron microscope was a TECNALG2F20 (200kV) from FEI Corporation, USA. The test conditions were as follows: the sample was pressed directly onto a sample stage containing conductive tape, and then the electron microscope was inserted for observation.

[0083] In the context of this invention specification, including the following embodiments, the median particle size of the modified graphene was obtained by dynamic light scattering characterization using a Malvern Panalytical MS-3000 laser particle size analyzer. Test conditions: The sample was dispersed in deionized water at a concentration of 0.01 mg / ml, and tested after sonication for 10 minutes. The instrument's light-blocking setting was set between 5% and 20%.

[0084] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0085] In the following embodiments, the coatings are applied using a two-coat spraying process, with a 3-hour interval between the two sprays, and the coating thickness is 60 μm.

[0086] Preparation Example 1 (1) Take 50g of graphene oxide powder and add it to 1kg of N,N-dimethylformamide. Disperse it by ultrasonication to obtain a graphene oxide dispersion. Add 1.5g of diphenylsilane to the dispersion in step (1), stir evenly, and slowly add 3g of tetraethylenepentamine to the mixture. Control the reaction temperature at 100℃ and the reflux reaction time at 60min. Filter the reacted material, wash with alcohol and water to obtain aminated graphene. (2) Take 50g of the amide graphene from step (1) and disperse it in deionized water. Sonicate it to obtain a uniform dispersion. Add 18g of phytic acid to the dispersion and reflux it at 80℃ for 5h. Then wash and filter it with water and freeze dry it to obtain phytic acid and amide co-modified graphene powder. According to X-ray photoelectron spectroscopy, the modified graphene contains 48.1% carbon, 7.6% nitrogen, 12.6% phosphorus, and 31.7% oxygen.

[0087] The median particle size of the modified graphene is 12 μm.

[0088] In Example 1, the infrared spectra of graphene oxide, amide graphene, and modified graphene are as follows: Figure 1 As shown. From Figure 1 It can be seen that, compared to graphene oxide, amide graphene has a lower content of 3461 cm⁻¹. -1 and 952 cm -1 Stretching vibration peaks belonging to NH and C-NH2 appeared at 1470 cm⁻¹, indicating that amide groups were successfully grafted onto graphene. Meanwhile, at 1470 cm⁻¹... -1 The presence of a characteristic peak for vinyl groups at this location indicates that organic amines are grafted onto graphene oxide via amide bonds. A peak at 3390 cm⁻¹ appears on the modified graphene. -1A hydroxyl peak of a phosphate group appears at 1641 cm⁻¹. -1 The characteristic peak of the six-membered carbon ring of phytic acid appears at 1555 cm⁻¹; simultaneously, at 1555 cm⁻¹... -1 The presence of an ammonium salt peak indicates that phosphate groups were grafted onto the surface of ammonium-treated graphene in the form of ammonium salts.

[0089] Figure 2 The image shows the X-ray photoelectron spectrum of the modified graphene in Example 1. The image confirms the presence of the N1s signal peak and the P1p signal peak generated by phytic acid grafting in the modified graphene. Both the surface amide functional group and the P element were grafted onto the graphene oxide.

[0090] Figure 3 This is the N1s X-ray photoelectron spectrum of the modified graphene in Example 1. The figure confirms the presence of the amide functional group O=C-NH (399.8 eV), as well as C-NH-C (399.1 eV), -C=NH (398.9 eV), and NC (395.7 eV) functional groups.

[0091] Figure 4 This is the P2p X-ray photoelectron spectrum of the modified graphene in Example 1. The figure confirms the presence of both the P(O)-N (135.8 eV) functional group and the -P=O (135 eV) and OPO (133.8 eV) functional groups.

[0092] The above spectral structures collectively demonstrate that graphene oxide was modified and grafted with tetraethylenepentamine to form aminated graphene, and then the combination of phytic acid and the amine groups of tetraethylenepentamine formed a stable modified graphene structure. This structure not only ensures the uniform dispersion of graphene in the coating solvent, but also leverages the combined effect of the phytic acid groups and graphene to improve the overall performance of the coating.

[0093] Preparation Example 2 (1) Take 50g of graphene oxide powder, add it to 1kg of N-methylpyrrolidone, and disperse it by ultrasonication to obtain a graphene oxide dispersion; add 1.5g of phenyltriazole to the dispersion in step (1), stir evenly, slowly add 1g of ethylenediamine to the mixture, control the reaction temperature at 60℃, and reflux for 30min; filter the reacted material, wash with alcohol and water to obtain aminated graphene; (2) Take 50g of the amide graphene from step (1) and disperse it in deionized water. Sonicate it to obtain a uniform dispersion. Add 5g of phytic acid to the dispersion and reflux it at 60℃ for 3h. Then wash and filter it with water and freeze dry it to obtain phytic acid and amide co-modified graphene powder. The median particle size of the modified graphene is 5 μm.

[0094] According to X-ray photoelectron spectroscopy, the modified graphene contains 59.3% carbon, 5.6% nitrogen, 7.4% phosphorus, and 27.7% oxygen.

[0095] Preparation Example 3 (1) Take 50g of graphene oxide powder, add it to 1kg of N,N-dimethylformamide, and disperse it by ultrasonication to obtain a graphene oxide dispersion; add 2g of methyl orthosilicate to the dispersion in step (1), stir evenly, slowly add 3.5g of diethylenetriamine to the mixture, control the reaction temperature at 90℃, and reflux the reaction for 120min; filter the reaction mixture, wash with alcohol and water to obtain aminated graphene; (2) Take 50g of the amide graphene from step (1) and disperse it in deionized water. Sonicate it to obtain a uniform dispersion. Add 30g of phytic acid to the dispersion and reflux it at 80℃ for 6h. Then wash and filter it with water and freeze dry it to obtain phytic acid and amide co-modified graphene powder. Infrared spectrum of modified graphene and Figure 1 Similarly, this indicates that organic amines are grafted onto graphene oxide in the form of amide bonds, and phosphate groups are grafted onto the surface of ammonium-based graphene oxide in the form of ammonium salts.

[0096] The median particle size of the modified graphene is 5 micrometers.

[0097] According to X-ray photoelectron spectroscopy, the modified graphene contains 57.3% carbon, 11.6% nitrogen, 14.6% phosphorus, and 16.5% oxygen.

[0098] Example 1 (1) Take 2 parts of phytic acid and amide co-modified graphene from Preparation Example 1, 20 parts of waterborne alkyd resin (FX-6001), 0.2 parts of 2-amino-2-methyl-1-propanol, 6 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 7 parts of titanium dioxide, 4 parts of aluminum tripolyphosphate, 9 parts of mica powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 60 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 500 rpm for 60 min, and the fineness is ≤25μm.

[0099] (2) After grinding the product in step (1), add 2 parts of organosilicon dispersant (Tego-410), 0.03 parts of vanadium isooctanoate with a vanadium content of 4wt%, 5 parts of bentonite, 3 parts of zinc oxide, 1 part of talc powder, and 17.57 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1300 rpm for 10 min, then transfer to a sand mill and grind at 500 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0100] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0101] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying the coating was 15min, and the skinning test within 48h was qualified; it passed the water resistance test for 150h and the neutral salt spray resistance test for 300h.

[0102] Example 2 (1) Take 1.5 parts of phytic acid and amide co-modified graphene from Preparation Example 2, 28 parts of waterborne alkyd resin (FX-6001), 0.2 parts of ethanolamine, 3 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 8 parts of calcium carbonate, 6 parts of aluminum tripolyphosphate, 5 parts of mica iron oxide, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1500 rpm, shear and disperse for 30 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 600 rpm for 30 min, and the fineness is ≤25μm.

[0103] (2) After grinding, add 1 part of organosilicon dispersant (Tego-800), 0.08 parts of vanadium isooctanoate with a vanadium content of 4wt%, 6 parts of bentonite, 5 parts of barium sulfate, 1 part of carbon black, and 15.02 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1000 rpm for 50 min. Transfer to a sand mill and grind at 400 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0104] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0105] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 62%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying was 13min, and the skinning test within 48h was qualified; it passed the water resistance test for 133h and the neutral salt spray resistance test for 265h.

[0106] Example 3 (1) Take 2.7 parts of phytic acid and amide co-modified graphene from Preparation Example 3, 15 parts of waterborne alkyd resin (FX-6001), 0.13 parts of butanolamine, 7 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 6 parts of titanium dioxide, 7 parts of calcium carbonate, 1 part of mica powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 30 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 600 rpm for 30 min, and the fineness is ≤25μm.

[0107] (2) After grinding the product in step (1), add 4.5 parts of organosilicon dispersant (Tego-100), 0.01 parts of vanadium isooctanoate with a vanadium content of 4wt%, 2 parts of bentonite, 1 part of barium sulfate, 1 part of talc powder, and 27.66 parts of deionized water to a high-speed shear mixer. Shear and disperse at 800 rpm for 30 min, then transfer to a sand mill and grind at 600 rpm for 10 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0108] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0109] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 47%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying the coating was 20min, and the skinning test within 48h was qualified; it passed the water resistance test for 161h and the neutral salt spray resistance test for 330h.

[0110] Example 4 (1) Take 5 parts of phytic acid and amide co-modified graphene from Preparation Example 1, 20 parts of waterborne alkyd resin (FX-6001), 0.2 parts of 2-amino-2-methyl-1-propanol, 6 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 7 parts of titanium dioxide, 4 parts of aluminum tripolyphosphate, 9 parts of mica powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 60 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product to a sand mill, grind at 500 rpm for 60 min, and the fineness is ≤25μm.

[0111] (2) After grinding the product in step (1), add 2 parts of organosilicon dispersant (Tego-410), 0.03 parts of vanadium isooctanoate with a vanadium content of 4wt%, 5 parts of bentonite, 3 parts of zinc oxide, 1 part of talc powder, and 12.77 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1300 rpm for 10 min, then transfer to a sand mill and grind at 500 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0112] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0113] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 62%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 6MPa; the surface drying time of the coating obtained by spraying was 25min, and the skinning test within 96h was qualified; it passed the water resistance test for 120h and the neutral salt spray resistance test for 360h.

[0114] Example 5 (1) Take 2 parts of phytic acid and amide co-modified graphene from Preparation Example 1, 35 parts of waterborne alkyd resin (FX-6001), 0.2 parts of 2-amino-2-methyl-1-propanol, 6 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 7 parts of titanium dioxide, 4 parts of aluminum tripolyphosphate, 9 parts of mica powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 60 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 500 rpm for 60 min, and the fineness is ≤25μm.

[0115] (2) After grinding the product in step (1), add 2 parts of organosilicon dispersant (Tego-410), 0.03 parts of vanadium isooctanoate with a vanadium content of 4wt%, 5 parts of bentonite, 3 parts of zinc oxide, 1 part of talc powder, and 17.57 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1300 rpm for 10 min, then transfer to a sand mill and grind at 500 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0116] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0117] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 64%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying was 30min, and the skinning test within 48h was qualified; it passed the water resistance test for 180h and the neutral salt spray resistance test for 245h.

[0118] Example 6 (1) Take 2 parts of phytic acid and amide co-modified graphene from Preparation Example 1, 20 parts of waterborne alkyd resin (FX-6001), 0.2 parts of 2-amino-2-methyl-1-propanol, 6 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 2 parts of titanium dioxide, 1 part of aluminum tripolyphosphate, 2 parts of mica powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 60 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 500 rpm for 60 min, and the fineness is ≤25μm.

[0119] (2) After grinding the product in step (1), add 2 parts of organosilicon dispersant (Tego-410), 0.03 parts of vanadium isooctanoate with a vanadium content of 4wt%, 3 parts of bentonite, 2 parts of zinc oxide, 1 part of talc powder, and 17.57 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1300 rpm for 10 min, then transfer to a sand mill and grind at 500 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0120] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0121] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 49%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying the coating was 12min, and the skinning test within 96h was qualified; it passed the water resistance test for 160h and the neutral salt spray resistance test for 220h.

[0122] Example 7 (1) Take 2 parts of phytic acid and amide co-modified graphene from Preparation Example 1, 20 parts of waterborne alkyd resin (FX-6001), 0.2 parts of 2-amino-2-methyl-1-propanol, 6 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 7 parts of titanium dioxide, 4 parts of aluminum tripolyphosphate, 9 parts of mica powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 60 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 500 rpm for 60 min, and the fineness is ≤25μm.

[0123] (2) After grinding the product in step (1), add 2 parts of organosilicon dispersant (Tego-410), 0.2 parts of vanadium isooctanoate with a vanadium content of 4wt%, 5 parts of bentonite, 3 parts of zinc oxide, 1 part of talc powder, and 15.6 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1300 rpm for 10 min, then transfer to a sand mill and grind at 500 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0124] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0125] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying the coating was 10min, and the skinning test within 48h was qualified; it passed the water resistance test for 130h and the neutral salt spray resistance test for 230h.

[0126] Example 8 The method of Example 1 was followed, except that the aqueous alkanolamine resin was not added, but replaced with an equal amount of aqueous acrylic resin (HF-05A), and the results are shown in Table 1.

[0127] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 4MPa; the surface drying time of the coating obtained by spraying was 25min, and the skinning test within 96h was qualified; it passed the 200h water resistance test and the 190h neutral salt spray resistance test.

[0128] Example 9 (1) Take 2 parts of phytic acid and amide co-modified graphene from Preparation Example 1, 20 parts of waterborne alkyd resin (FX-6001), 0.2 parts of 2-amino-2-methyl-1-propanol, 6 parts of polyurethane thickener (DS-7216S, viscosity 6000mPa•s), 7 parts of titanium dioxide, 4 parts of aluminum tripolyphosphate, 9 parts of mica powder, 5 parts of bentonite, 3 parts of zinc oxide, 1 part of talc powder, and 25 parts of deionized water, add them to a high-speed shear mixer, adjust the speed to 1200 rpm, shear and disperse for 60 min, control the shear temperature to 40℃, until all solids are evenly dispersed and no stratification occurs; transfer the sheared product into a sand mill, grind at 500 rpm for 60 min, and the fineness is ≤25μm.

[0129] (2) After grinding the product in step (1), add 2 parts of organosilicon dispersant (Tego-410), 0.03 parts of vanadium isooctanoate with a vanadium content of 4wt%, and 17.57 parts of deionized water to a high-speed shear mixer. Shear and disperse at 1300 rpm for 10 min, then transfer to a sand mill and grind at 500 rpm for 30 min. The fineness is ≤30μm, and the graphene waterborne anti-corrosion coating is obtained.

[0130] (3) The graphene water-based anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying at a pressure of 0.6 MPa.

[0131] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 5MPa; the surface drying time of the coating obtained by spraying was 15min, and the skinning test within 48h was qualified; it passed the water resistance test for 140h and the neutral salt spray resistance test for 300h.

[0132] Comparative Example 1 The method of Example 1 was followed, except that phytic acid and amide co-modified graphene was not added, but replaced with an equal amount of carbon black. The results are shown in Table 1.

[0133] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 3MPa; the surface drying time of the coating obtained by spraying was 35min, and the skinning test within 48h was qualified; it passed the 30h water resistance test and the 24h neutral salt spray resistance test.

[0134] Comparative Example 2 The method of Example 1 was followed, except that 2-amino-2-methyl-1-propanol was not added, but replaced with an equal amount of water. The results are shown in Table 1.

[0135] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 2MPa; the surface drying time of the coating obtained by spraying was 38min, and the skinning test within 12h was qualified; it passed the water resistance test for 15h and the neutral salt spray resistance test for 10h.

[0136] Comparative Example 3 The method of Example 1 was followed, except that vanadium isooctanoate was not added and was replaced with an equal amount of water. The results are shown in Table 1.

[0137] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 59%±1%; the adhesion of the graphene waterborne anticorrosive coating was 5MPa; the surface drying time of the coating obtained by spraying was 120min; the skinning test within 48h was qualified; the water resistance test was passed for 150h; and the neutral salt spray resistance test was passed for 210h.

[0138] Comparative Example 4 The method of Example 1 was followed, except that no polyurethane thickener was added and instead, an equal amount of water was used. The results are shown in Table 1.

[0139] The coating was tested using the aforementioned test standards: the solid content of the obtained coating was 53%±1%, the adhesion of the graphene waterborne anti-corrosion coating was 2MPa; the surface drying time of the coating obtained by spraying was 33min, and the skinning test within 48h was qualified; it passed the water resistance test for 15h and the neutral salt spray resistance test for 24h.

[0140] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A graphene waterborne anticorrosive material, characterized by, The graphene waterborne anticorrosive material includes a graphene waterborne anticorrosive coating, wherein the graphene waterborne anticorrosive coating comprises, by weight, 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drier, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, and 10-50 parts filler; The modified graphene comprises graphene oxide and ammonium phytate grafted onto the surface of graphene oxide via amide bonds, the structure of which is shown in formula (I). （I）， In formula (I), * represents the N-linked site in the amide bond; R1 is selected from one of the groups formed by removing two terminal amino groups from C2-C10 alkylene or n-ethylene(n+1)amines, where n is an integer and 2≤n≤6.

2. The graphene-based water-based anti-corrosion material according to claim 1, wherein, 1-3 parts by weight of modified graphene; and / or 10-30 parts by weight of epoxy resin; and / or By weight, 0.01-0.1 parts of cobalt-free drying agent; and / or The filler is 15-40 parts by weight.

3. The graphene-based waterborne anti-corrosion material according to claim 1 or 2, wherein, The adhesion of the graphene water-based anti-corrosion coating is ≥3MPa, preferably 4-6 MPa; and / or The thickness of the graphene water-based anti-corrosion coating is 30-80 μm; and / or The graphene water-based anti-corrosion coating does not contain zinc or cobalt.

4. The graphene-based waterborne anti-corrosion material according to any one of claims 1-3, wherein, The modified graphene contains 35wt%-60wt% carbon; and / or The modified graphene contains 1wt%-5wt% nitrogen by mass; and / or The modified graphene contains 1wt%-5wt% phosphorus; and / or The modified graphene contains 10wt%-35wt% oxygen by mass; and / or The median particle size of the modified graphene is 5 μm-15 μm; and / or R1 is selected from one of the groups formed by removing two terminal amino groups from a C2-C6 alkylene group or an n-ethylene (n+1)amine, where n is an integer and 2≤n≤5. Preferably, R1 is selected from one of ethylene, hexane, -CH2CH2NHCH2CH2-, -CH2CH2NHCH2CH2NHCH2CH2-, and -CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-.

5. The graphene-based waterborne anti-corrosion material according to any one of claims 1-4, wherein, The cobalt-free drying agent contains vanadium, preferably vanadium isooctanoate, and more preferably, the vanadium content in the cobalt-free drying agent is not less than 2.5 wt%, preferably 3-7 wt%; and / or The epoxy resin is selected from one or more of acrylic resins, alkyd resins, and polyurethane resins, preferably alkyd resins; and / or The alkanolamine is selected from one or more of 2-amino-2-methyl-1-propanol, ethanolamine, and butanolamine; and / or The polyurethane thickener has a viscosity of 1000-10000 mPa•s at 25°C; and / or The organosilicon dispersant is selected from one or more polyether siloxane copolymer dispersants, preferably from one or more of Tego-100, Tego-260, Tego-270, Tego-280, Tego-410, and Tego-800; and / or The filler is selected from one or more of the following: aluminum tripolyphosphate, barium sulfate, titanium dioxide, carbon black, calcium carbonate, flake glass, bentonite, talc, zinc oxide, mica powder, and mica iron oxide. The preferred packing material is selected from packing material 1 and packing material 2, wherein, Filler 1 is selected from one or more of aluminum tripolyphosphate, titanium dioxide, mica powder, mica iron oxide, calcium carbonate, and flake glass; Filler 2 is selected from one or more of bentonite, talc, zinc oxide, barium sulfate, and carbon black; Preferably, packing 1 accounts for 40-80 wt% of the total weight of the packing, and packing 2 accounts for 20-60 wt% of the total weight of the packing.

6. A graphene aqueous anticorrosive coating, characterized by, The coating includes: By weight, the composition includes 0.5-5 parts modified graphene, 5-40 parts epoxy resin, 0.01-0.2 parts cobalt-free drying agent, 0.1-0.5 parts alkanolamine, 0.5-5 parts organosilicon dispersant, 2-8 parts polyurethane thickener, 10-50 parts filler, and 20-55 parts deionized water. The modified graphene comprises graphene oxide and ammonium phytate grafted onto the surface of graphene oxide via amide bonds, the structure of which is shown in formula (I). （I）， In formula (I), * represents the N-linked site in the amide bond; R1 is selected from one of the groups formed by removing two terminal amino groups from C2-C10 alkylene or n-ethylene(n+1)amines, where n is an integer and 2≤n≤6; Preferably, the coating comprises: 1-3 parts by weight of modified graphene; and / or 10-30 parts by weight of epoxy resin; and / or By weight, 0.01-0.1 parts of cobalt-free drying agent; and / or The filler is 15-40 parts by weight.

7. The graphene-based waterborne anti-corrosion coating according to claim 6, wherein, The modified graphene contains 35wt%-60wt% carbon; and / or The modified graphene contains 1wt%-5wt% nitrogen by mass; and / or The modified graphene contains 1wt%-5wt% phosphorus; and / or The modified graphene contains 10wt%-35wt% oxygen by mass; and / or The median particle size of the modified graphene is 5 μm-15 μm; and / or R1 is selected from one of ethylidene, hexylidene, -CH2CH2NHCH2CH2-, -CH2CH2NHCH2CH2NHCH2CH2-, and -CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-; and / or The cobalt-free drying agent contains vanadium, preferably vanadium isooctanoate, and more preferably, the vanadium content in the cobalt-free drying agent is not less than 2.5 wt%, preferably 3-7 wt%; and / or The epoxy resin is selected from one or more of acrylic resins, alkyd resins, and polyurethane resins, preferably alkyd resins; and / or The alkanolamine is selected from one or more of 2-amino-2-methyl-1-propanol, ethanolamine, and butanolamine; and / or The polyurethane thickener has a viscosity of 1000-10000 mPa•s at 25°C; and / or The organosilicon dispersant is selected from one or more polyether siloxane copolymer dispersants, preferably from one or more of Tego-100, Tego-260, Tego-270, Tego-280, Tego-410, and Tego-800; and / or The filler is selected from one or more of the following: aluminum tripolyphosphate, barium sulfate, titanium dioxide, carbon black, calcium carbonate, flake glass, bentonite, talc, zinc oxide, mica powder, and mica iron oxide. The preferred packing material is selected from packing material 1 and packing material 2, wherein, Filler 1 is selected from one or more of aluminum tripolyphosphate, titanium dioxide, mica powder, mica iron oxide, calcium carbonate, and flake glass; Filler 2 is selected from one or more of bentonite, talc, zinc oxide, barium sulfate, and carbon black; Preferably, packing 1 accounts for 40-80 wt% of the total weight of the packing, and packing 2 accounts for 20-60 wt% of the total weight of the packing; and / or The solid mass fraction of the graphene waterborne anti-corrosion coating is 45wt%-65wt%.

8. The graphene aqueous anticorrosive coating according to claim 6 or 7, wherein, The method for preparing the modified graphene includes: (1) in the presence of a first solvent and an amidation catalyst, an organic amine is subjected to an amidation reaction with graphene oxide to separate and obtain amidated graphene. (2) In the presence of a second solvent, phytic acid is contacted with aminated graphene, separated, and the solid is dried; the organic amine is selected from one or more of C2-C10 organic diamines and C2-C6 organic polyamines, preferably one or more of triethylenetetramine, hexamethylenediamine, ethylenediamine, tetraethylenepentamine, and diethylenetriamine; and / or The mass ratio of organic amine to graphene oxide is 0.02-0.1:1; and / or The mass ratio of phytic acid to aminated graphene is 0.1-0.7:

1.

9. Process for the preparation of a graphene aqueous anticorrosive paint according to any one of claims 6-8, characterized by, The method includes: mixing the components of the coating; Preferably, the preparation method includes: (1) After mixing modified graphene, epoxy resin, alkanolamine, polyurethane thickener, filler 1 and deionized water, the mixture undergoes first shearing and first grinding. (2) The product of step (1) is mixed with filler 2, cobalt-free drying agent, organosilicon dispersant and deionized water, and then subjected to second shearing and second grinding.

10. A graphene aqueous anticorrosive coating, characterized by, The graphene waterborne anti-corrosion coating is prepared by the graphene waterborne anti-corrosion coating according to any one of claims 6-8.

11. The application of the graphene waterborne anti-corrosion material according to any one of claims 1-5, the graphene waterborne anti-corrosion coating according to any one of claims 6-8, or the graphene waterborne anti-corrosion coating according to claim 10 in the petroleum, chemical, power, and electronics industries.

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