Preparation method and application of an aqueous high-solid graphene zinc heavy-duty anticorrosive coating

Abstract

The present invention discloses a preparation method and application of a waterborne high-solid graphene zinc heavy-duty anti-corrosion coating, which relates to the technical field of anti-corrosion coatings. The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating comprises the following raw materials in parts by weight: 20-40 parts of waterborne epoxy resin, 10-20 parts of zinc powder, 0.1-0.5 part of modified graphene oxide, 5-15 parts of filler, 0.1-1 part of dispersant, 0.1-0.5 part of film-forming aid, 5-10 parts of deionized water, and 1-10 parts of curing agent. The anti-corrosion coating of the present invention has excellent anti-corrosion performance and adhesion.

Description

Technical Field

[0001] The invention relates to the technical field of anti-corrosion coatings, and in particular to a preparation method and application of a water-based high-solid graphene zinc heavy-duty anti-corrosion coating. Background Art

[0002] Metal corrosion is a global problem, causing huge economic losses every year. It is estimated that about 20% of the world's metal materials cannot be recycled due to corrosion, and the marine corrosion environment is particularly harsh. Traditional anti-corrosion coatings mainly include epoxy resin coatings, alkyd resin coatings, polyurethane coatings, acrylic resin coatings and zinc-rich coatings. Among these coatings, zinc-rich coatings are widely used in the field of heavy corrosion protection of steel structures due to their cathodic protection effect, protecting the base metal through the sacrificial anode effect of zinc powder. However, traditional zinc-rich coatings have problems such as high zinc powder content (usually accounting for more than 80% of the dry film weight), thick coatings, and serious environmental pollution.

[0003] In recent years, with the increasing environmental protection requirements, water-based paint has become the development direction of the paint industry due to its advantages of being non-toxic, harmless, energy-saving and environmentally friendly. However, single-component water-based paints are often difficult to meet the anti-corrosion requirements under complex working conditions, and need to be modified with nanoparticles or mixed for use.

[0004] As a new type of two-dimensional nanomaterial, graphene has excellent physical and chemical properties, including high specific surface area, excellent electrical and thermal conductivity, outstanding mechanical strength and unique barrier properties. These properties make it an ideal material for improving the performance of anti-corrosion coatings. Studies have shown that graphene plays a role in anti-corrosion coatings mainly through three mechanisms: first, its layered structure forms a "maze-like" shielding effect, extending the penetration path of the corrosive medium; second, its high electron mobility promotes the formation of a conductive network between zinc powders, improving the efficiency of cathodic protection; third, its surface functional groups can form cross-links with the resin matrix to enhance the adhesion of the coating.

[0005] Therefore, the object of the present invention is to develop a new graphene anti-corrosion coating with excellent anti-corrosion performance. Summary of the invention

[0006] Based on the technical problems existing in the background technology, the present invention proposes a preparation method and application of a water-based high-solid graphene zinc heavy-duty anti-corrosion coating, which has excellent anti-corrosion performance and adhesion.

[0007] The water-based high-solid graphene zinc heavy-duty anti-corrosion coating provided by the present invention comprises the following raw materials in parts by weight: 20-40 parts of water-based epoxy resin, 10-20 parts of zinc powder, 0.1-0.5 parts of modified graphene oxide, 5-15 parts of filler, 0.1-1 parts of dispersant, 0.1-0.5 parts of film-forming aid, 5-10 parts of deionized water and 1-10 parts of curing agent.

[0008] Preferably, the preparation method of the modified graphene oxide is as follows: graphene oxide is dispersed in deionized water, then phenylaminomethyltriethoxysilane is added for reaction, and after the reaction, polyetheramine is added for ultrasonic treatment to obtain the modified graphene oxide.

[0009] Preferably, the mass ratio of graphene oxide, phenylaminomethyltriethoxysilane and polyetheramine is 1:1 - 2:0.8 - 1.2; the reaction temperature is 50 - 70 °C, the time is 4 - 6 h, and the pH is 3 - 4; the power of ultrasonic treatment is 300 - 500 W, the time is 1 - 2 h, and the temperature is 40 - 60 °C.

[0010] Preferably, the filler is one or more of mica powder, barium sulfate, talc powder, silica powder, kaolin, fumed silica and calcium carbonate.

[0011] Preferably, the film-forming aid is one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, propylene glycol phenyl ether, ethylene glycol butyl ether and Texanol ester alcohol.

[0012] Preferably, the curing agent is one or more of Jeffamine D-230, Anquamine 419, Cardolite NC-541, Versamid 125, Mannich base curing agent and waterborne isophorone diamine derivative.

[0013] Preferably, the dispersant is composed of a silane coupling agent-modified hyperbranched polyester dispersant and a modified polycarboxylate dispersant in a mass ratio of 1:1 - 5.

[0014] Preferably, the preparation method steps of the silane coupling agent-modified hyperbranched polyester dispersant are as follows:

[0015] S1: Add 2,2-dimethylolpropionic acid, pentaerythritol, N-methylpyrrolidone, p-toluenesulfonic acid and antioxidant into a reaction vessel, and react at 100 - 140 °C for 1 - 3 h under an inert atmosphere; then raise the temperature to 160 - 200 °C and continue to react until the acid value of the reaction system is lower than 5 mgKOH / g. After the reaction, neutralize, precipitate, wash and dry to obtain hyperbranched polyester;

[0016] S2: Dissolve γ-glycidoxypropyltrimethoxysilane in methanol, and then add hyperbranched polyester and dibutyltin dilaurate in sequence for reaction to obtain the silane coupling agent-modified hyperbranched polyester dispersant.

[0017] Preferably, the mass ratio of 2,2 - dimethylolpropionic acid, pentaerythritol, p - toluenesulfonic acid and antioxidant is 100:10 - 30:0.5 - 1.5:0.1 - 0.3; the mass ratio of hyperbranched polyester, γ - glycidoxypropyltrimethoxysilane and dibutyltin dilaurate is 100:30 - 50:0.5 - 1.

[0018] Preferably, the preparation method of the modified polycarboxylate dispersant is as follows: allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate are sequentially added into 2 - acrylamide - 2 - methylpropanesulfonic acid for reaction to obtain the modified polycarboxylate dispersant.

[0019] Preferably, the mass ratio of 2 - acrylamide - 2 - methylpropanesulfonic acid, allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate is 10:0.8 - 1.2:0.4 - 0.6:0.5 - 1.

[0020] Preferably, the reaction conditions are: temperature 70 - 90 °C, time 2 - 4 h.

[0021] The preparation method of a water - borne high - solid graphene zinc heavy - duty anti - corrosion coating provided by the present invention, the water - borne high - solid graphene zinc heavy - duty anti - corrosion coating is as described above, and is characterized in that the method steps are as follows: an aqueous epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film - forming aid and deionized water are mixed evenly, and then a curing agent is added and mixed evenly to obtain the water - borne high - solid graphene zinc heavy - duty anti - corrosion coating.

[0022] The application of the above - mentioned water - borne high - solid graphene zinc heavy - duty anti - corrosion coating provided by the present invention in metal anti - corrosion.

[0023] The beneficial technical effects of the present invention:

[0024] (1) In the present invention, graphene oxide is modified by phenylaminomethyltriethoxysilane and polyetheramine, which not only improves the dispersibility of the modified graphene oxide, but also forms chemical bonding with zinc powder, filler and resin through silane coupling, enhancing the denseness and adhesion of the coating; the polyetheramine chain on the modified graphene oxide can also form a synergistic steric hindrance layer with the modified polycarboxylate dispersant, further improving the anti - corrosion performance of the coating; the phenylamino group of the modified graphene oxide forms a coordination bond with the surface of the substrate metal, and together with the high cross - linking density of the curing agent, can further improve the adhesion of the coating.

[0025] (2) The dispersant of the present invention is composed of a silane - coupling - agent - modified hyperbranched polyester dispersant and a modified polycarboxylate dispersant, which can not only improve the dispersion effect of modified graphene oxide and zinc powder, etc., but also construct a dense anti - corrosion barrier through chemical bonding and other methods, playing a synergistic promoting role in improving the anti - corrosion performance of the coating. Specific embodiments

[0026] The present invention will be further described below in conjunction with specific embodiments.

[0027] The waterborne epoxy resin (model S-990, solid content 70%) in the embodiments of the present invention is purchased from Qingdao Wanjiahuixin Surface Materials Technology Co., Ltd.; allyl polyoxyethylene ether (Mn = 2000) and other raw materials are all commercially available.

[0028] Example 1

[0029] The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating proposed by the present invention comprises the following raw materials in parts by weight: 30 parts of waterborne epoxy resin, 15 parts of zinc powder, 0.3 part of modified graphene oxide, 10 parts of filler, 0.5 part of dispersant, 0.3 part of film-forming aid, 8 parts of deionized water, and 5 parts of curing agent.

[0030] The preparation method of the modified graphene oxide is as follows: Disperse graphene oxide in deionized water, then add phenylaminomethyltriethoxysilane for reaction, and then add polyetheramine for ultrasonic treatment after the reaction to obtain modified graphene oxide.

[0031] The mass ratio of graphene oxide, phenylaminomethyltriethoxysilane and polyetheramine is 1:1.5:1; the reaction temperature is 60 °C, the time is 5 h, the pH is 3; the power of ultrasonic treatment is 400 W, the time is 1.5 h, and the temperature is 50 °C.

[0032] The filler is composed of mica powder, talc powder and silica powder in a mass ratio of 1:1:0.2; the film-forming aid is dipropylene glycol butyl ether; the curing agent is Anquamine 419.

[0033] The dispersant is composed of a silane coupling agent-modified hyperbranched polyester dispersant and a modified polycarboxylate dispersant in a mass ratio of 1:3.

[0034] The method steps for preparing the silane coupling agent-modified hyperbranched polyester dispersant are as follows:

[0035] S1: Add 2,2-dimethylolpropionic acid, pentaerythritol, N-methylpyrrolidone, p-toluenesulfonic acid and antioxidant into a reaction vessel, react at 120 °C for 2 h under an inert atmosphere; then raise the temperature to 180 °C and continue to react until the acid value of the reaction system is lower than 5 mgKOH / g. After the reaction, neutralize, precipitate, wash and dry to obtain hyperbranched polyester;

[0036] S2: Dissolve γ-glycidoxypropyltrimethoxysilane in methanol, and then add hyperbranched polyester and dibutyltin dilaurate in sequence for reaction to obtain the silane coupling agent-modified hyperbranched polyester dispersant.

[0037] The mass ratio of 2,2-dimethylolpropionic acid, pentaerythritol, p-toluenesulfonic acid and antioxidant is 100:20:1:0.2; the mass ratio of hyperbranched polyester, γ-glycidoxypropyltrimethoxysilane and dibutyltin dilaurate is 100:40:0.8.

[0038] The preparation method of the modified polycarboxylate dispersant is as follows: allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate are successively added to 2-acrylamide-2-methylpropanesulfonic acid for reaction to obtain the modified polycarboxylate dispersant.

[0039] The mass ratio of 2-acrylamide-2-methylpropanesulfonic acid, allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate is 10:1:0.5:0.8; the reaction conditions are: temperature 80 °C, time 3 h.

[0040] The waterborne epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film-forming aid and deionized water are mixed evenly, and then the curing agent is added and mixed evenly to obtain the waterborne high-solid graphene zinc heavy-duty anti-corrosion coating A1.

[0041] Example 2

[0042] The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating proposed by the present invention comprises the following raw materials in parts by weight: 20 parts of waterborne epoxy resin, 10 parts of zinc powder, 0.1 part of modified graphene oxide, 5 parts of filler, 0.1 part of dispersant, 0.1 part of film-forming aid, 5 parts of deionized water, and 1 part of curing agent.

[0043] The preparation method of the modified graphene oxide is as follows: graphene oxide is dispersed in deionized water, and then phenylaminomethyltriethoxysilane is added for reaction, and after the reaction, polyetheramine is added for ultrasonic treatment to obtain the modified graphene oxide.

[0044] The mass ratio of graphene oxide, phenylaminomethyltriethoxysilane and polyetheramine is 1:1:0.8; the reaction temperature is 50 °C, the time is 6 h, and the pH is 3; the power of ultrasonic treatment is 300 W, the time is 2 h, and the temperature is 40 °C.

[0045] The filler is fumed silica; the film-forming aid is Texanol ester alcohol; the curing agent is Jeffamine D-230.

[0046] The dispersant is composed of a silane coupling agent-modified hyperbranched polyester dispersant and a modified polycarboxylate dispersant in a mass ratio of 1:1.

[0047] The method steps for preparing the silane coupling agent-modified hyperbranched polyester dispersant are as follows:

[0048] S1: Add 2,2 - dimethylolpropionic acid, pentaerythritol, N - methylpyrrolidone, p - toluenesulfonic acid and antioxidant into a reaction vessel, and react at 100 °C for 3 h under an inert atmosphere; then raise the temperature to 160 °C and continue to react until the acid value of the reaction system is lower than 5 mgKOH / g. After the reaction, neutralize, precipitate, wash and dry to obtain hyperbranched polyester.

[0049] S2: Dissolve γ - glycidoxypropyltrimethoxysilane in methanol, and then add hyperbranched polyester and dibutyltin dilaurate in sequence for reaction to prepare a silane coupling agent - modified hyperbranched polyester dispersant.

[0050] The mass ratio of 2,2 - dimethylolpropionic acid, pentaerythritol, p - toluenesulfonic acid and antioxidant is 100:10:0.5:0.1; the mass ratio of hyperbranched polyester, γ - glycidoxypropyltrimethoxysilane and dibutyltin dilaurate is 100:30:0.5.

[0051] The preparation method of the modified polycarboxylate - based dispersant is as follows: Add allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate into 2 - acrylamide - 2 - methylpropanesulfonic acid in sequence for reaction to prepare the modified polycarboxylate - based dispersant.

[0052] The mass ratio of 2 - acrylamide - 2 - methylpropanesulfonic acid, allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate is 10:0.8:0.4:0.5; the reaction conditions are: temperature 70 °C, time 4 h.

[0053] Mix water - borne epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film - forming aid and deionized water evenly, and then add a curing agent and mix evenly to prepare water - borne high - solid graphene zinc heavy - duty anti - corrosion coating A2.

[0054] Example 3

[0055] The water - borne high - solid graphene zinc heavy - duty anti - corrosion coating proposed by the present invention comprises the following raw materials in parts by weight: 40 parts of water - borne epoxy resin, 20 parts of zinc powder, 0.5 part of modified graphene oxide, 15 parts of filler, 1 part of dispersant, 0.5 part of film - forming aid, 10 parts of deionized water, and 10 parts of curing agent.

[0056] The preparation method of modified graphene oxide is as follows: Disperse graphene oxide in deionized water, then add phenylaminomethyltriethoxysilane for reaction, and then add polyetheramine for ultrasonic treatment to obtain modified graphene oxide.

[0057] The mass ratio of graphene oxide, phenylaminomethyltriethoxysilane and polyetheramine is 1:2:1.2; the reaction temperature is 70 °C, the time is 6 h, and the pH is 3; the power of ultrasonic treatment is 500 W, the time is 2 h, and the temperature is 40 °C.

[0058] The filler is talc powder; the film-forming aid is dipropylene glycol methyl ether; the curing agent is a waterborne isophorone diamine derivative.

[0059] The dispersant is composed of a silane coupling agent-modified hyperbranched polyester dispersant and a modified polycarboxylate dispersant in a mass ratio of 1:5.

[0060] The method for preparing the silane coupling agent-modified hyperbranched polyester dispersant is as follows:

[0061] S1: Add 2,2-dimethylolpropionic acid, pentaerythritol, N-methylpyrrolidone, p-toluenesulfonic acid, and antioxidant into a reaction vessel, react at 140 °C for 1 h under an inert atmosphere; then raise the temperature to 200 °C and continue to react until the acid value of the reaction system is lower than 5 mgKOH / g. After the reaction, neutralize, precipitate, wash, and dry to obtain hyperbranched polyester;

[0062] S2: Dissolve γ-glycidoxypropyltrimethoxysilane in methanol, and then sequentially add hyperbranched polyester and dibutyltin dilaurate for reaction to prepare the silane coupling agent-modified hyperbranched polyester dispersant.

[0063] The mass ratio of 2,2-dimethylolpropionic acid, pentaerythritol, p-toluenesulfonic acid, and antioxidant is 100:30:1.5:0.3; the mass ratio of hyperbranched polyester, γ-glycidoxypropyltrimethoxysilane, and dibutyltin dilaurate is 100:50:1.

[0064] The preparation method of the modified polycarboxylate dispersant is: sequentially add allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride, and potassium persulfate into 2-acrylamide-2-methylpropanesulfonic acid for reaction to prepare the modified polycarboxylate dispersant.

[0065] The mass ratio of 2-acrylamide-2-methylpropanesulfonic acid, allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride, and potassium persulfate is 10:1.2:0.6:1; the reaction conditions are: temperature 90 °C, time 2 h.

[0066] Mix the waterborne epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film-forming aid, and deionized water evenly, and then add the curing agent and mix evenly to prepare the waterborne high-solid graphene zinc heavy-duty anti-corrosion coating A3.

[0067] Comparative Example 1

[0068] The dispersant in this scheme is a silane coupling agent-modified hyperbranched polyester dispersant, and the other conditions are the same as those in Example 1.

[0069] The water-based epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film-forming aid and deionized water are mixed evenly, and then a curing agent is added and mixed evenly to prepare a water-based high-solid graphene zinc heavy-duty anti-corrosion coating A4.

[0070] Comparative Example 2

[0071] The dispersant of this solution is a modified polycarboxylic acid dispersant, and the other conditions are the same as those in Example 1.

[0072] The water-based epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film-forming aid and deionized water were mixed evenly, and then a curing agent was added and mixed evenly to prepare a water-based high-solid graphene zinc heavy-duty anti-corrosion coating A5.

[0073] The adhesion and anti-corrosion performance of the anti-corrosion coatings of Examples 1-3 and Comparative Examples 1-2 were tested, and the test results are shown in Table 1.

[0074] Among them, the corrosion resistance refers to GB / T1771-2007; the adhesion refers to ISO2409:2020.

[0075] Table 1 Anticorrosive coating performance test results

[0076] Group Adhesion Salt spray resistance (h) Example 1 Level 1 No blistering or peeling after 6500 h; chalking level 1, color change level 1 Example 2 Level 2 No blistering or peeling after 6000 h; chalking level 2, color change level 1 Example 3 Level 2 No blistering or peeling after 6000 h; chalking level 1, color change level 1 Comparative Example 1 Level 3 Slight blistering after 4000 h, no peeling; chalking level 2, color change level 2 Comparative Example 2 Level 4 Slight blistering after 3500 h, no peeling; chalking level 3, color change level 2

[0077] It can be seen from the test results in Table 1 that the anticorrosive coating of the present invention has excellent adhesion and anticorrosion effect. This is because the present invention modifies graphene oxide by using phenylaminomethyltriethoxysilane and polyetheramine, which not only improves the dispersibility of the modified graphene oxide, but also forms chemical bonds with zinc powder, filler and resin through silane coupling, thereby enhancing the compactness and adhesion of the coating; the polyetheramine chain on the modified graphene oxide can also form a synergistic steric hindrance layer with the modified polycarboxylic acid dispersant, thereby further improving the anticorrosion performance of the coating; the phenylamino group of the modified graphene oxide forms a coordination bond with the metal surface of the substrate, and the high crosslinking density of the curing agent can further improve the adhesion of the coating. It can be seen from the test results of Example 1 and Comparative Examples 1 and 2 that the dispersant of the present invention is composed of a silane coupling agent modified hyperbranched polyester dispersant and a modified polycarboxylic acid dispersant, which can not only improve the dispersion effect of modified graphene oxide and zinc powder, but also construct a dense anti-corrosion barrier through chemical bonding and the like, thereby achieving a synergistic promotion effect in improving the anti-corrosion performance of the coating.

[0078] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present application. The scope of the present application is defined by the appended claims and their equivalents, and all shall be included in the scope of protection of the present application.

Claims

1. A waterborne high-solid graphene zinc heavy-duty anti-corrosion coating, characterized in that, It contains the following raw materials by weight: 20 - 40 parts of waterborne epoxy resin, 10 - 20 parts of zinc powder, 0.1 - 0.5 part of modified graphene oxide, 5 - 15 parts of filler, 0.1 - 1 part of dispersant, 0.1 - 0.5 part of film-forming aid, 5 - 10 parts of deionized water, and 1 - 10 parts of curing agent; The preparation method of the modified graphene oxide is as follows: Disperse graphene oxide in deionized water, then add phenylaminomethyltriethoxysilane for reaction, and after the reaction, add polyetheramine for ultrasonic treatment to obtain modified graphene oxide; The dispersant is composed of a silane coupling agent-modified hyperbranched polyester dispersant and a modified polycarboxylate dispersant in a mass ratio of 1:1 - 5; The method steps for preparing the silane coupling agent-modified hyperbranched polyester dispersant are as follows: S1: Add 2,2-dimethylolpropionic acid, pentaerythritol, N-methylpyrrolidone, p-toluenesulfonic acid, and antioxidant into a reaction vessel, and react at 100 - 140 °C for 1 - 3 h under an inert atmosphere; then raise the temperature to 160 - 200 °C and continue the reaction until the acid value of the reaction system is lower than 5 mg KOH / g. After the reaction, neutralize, precipitate, wash, and dry to obtain hyperbranched polyester; S2: Dissolve γ-glycidoxypropyltrimethoxysilane in methanol, and then successively add hyperbranched polyester and dibutyltin dilaurate for reaction to obtain a silane coupling agent-modified hyperbranched polyester dispersant; The preparation method of the modified polycarboxylate dispersant is: Add allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride, and potassium persulfate into 2-acrylamide-2-methylpropanesulfonic acid for reaction to obtain a modified polycarboxylate dispersant.

2. The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating according to claim 1, wherein The mass ratio of graphene oxide, phenylaminomethyltriethoxysilane, and polyetheramine is 1:1 - 2:0.8 - 1.2; the reaction temperature is 50 - 70 °C, the time is 4 - 6 h, and the pH is 3 - 4; the power of ultrasonic treatment is 300 - 500 W, the time is 1 - 2 h, and the temperature is 40 - 60 °C.

3. The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating according to claim 1, characterized in that The filler is one or more of mica powder, barium sulfate, talc powder, silica powder, kaolin, fumed silica, and calcium carbonate; The film-forming aid is one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, propylene glycol phenyl ether, ethylene glycol butyl ether, and Texanol ester alcohol; The curing agent is one or more of Jeffamine D-230, Anquamine 419, Cardolite NC-541, Versamid 125, Mannich base curing agent, and waterborne isophorone diamine derivative; 4. The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating according to claim 1, wherein, The mass ratio of 2,2-dimethylolpropionic acid, pentaerythritol, p-toluenesulfonic acid, and antioxidant is 100:10 - 30:0.5 - 1.5:0.1 - 0.3; the mass ratio of hyperbranched polyester, γ-glycidoxypropyltrimethoxysilane, and dibutyltin dilaurate is 100:30 - 50:0.5 - 1.

5. The waterborne high-solid graphene zinc heavy-duty anti-corrosion coating according to claim 1, wherein The mass ratio of 2-acrylamide-2-methylpropanesulfonic acid, allyl polyoxyethylene ether, methacryloyloxyethyl trimethyl ammonium chloride and potassium persulfate is 10:0.8 - 1.2:0.4 - 0.6:0.5 - 1; the reaction conditions are: temperature 70 - 90 °C, time 2 - 4 h.

6. A preparation method of a waterborne high-solid graphene zinc heavy-duty anti-corrosion coating, the waterborne high-solid graphene zinc heavy-duty anti-corrosion coating being as described in any one of claims 1-5, characterized in that, The method steps are as follows: uniformly mix waterborne epoxy resin, zinc powder, modified graphene oxide, filler, dispersant, film-forming aid and deionized water, and then add a curing agent and mix uniformly to obtain a waterborne high-solid graphene zinc heavy-duty anti-corrosion coating.

7. The application of the waterborne high-solid graphene zinc heavy-duty anti-corrosion coating according to any one of claims 1 - 5 in metal anti-corrosion.