CN113512341A - Graphene oxide/epoxy vinyl ester resin heavy-duty anti-corrosion solvent-free composite coating and preparation method and application thereof - Google Patents
Graphene oxide/epoxy vinyl ester resin heavy-duty anti-corrosion solvent-free composite coating and preparation method and application thereof Download PDFInfo
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Abstract
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating as well as a preparation method and application thereof. According to the invention, firstly, half-blocking reaction of diisocyanate is carried out by using an acrylate monomer, then epoxy resin and unsaturated monoacid serving as a diluent are added, grafting reaction is carried out on isocyanate and hydroxyl on the epoxy resin, graphene oxide and dicarboxylic acid are added after the reaction is completed, functional groups on the graphene oxide participate in the reaction, and finally, blocking is carried out on the epoxy resin by using carboxylic acid, so that the graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating is obtained. The graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating has excellent barrier property, better corrosion resistance and excellent mechanical property, and no organic solvent is added in the reaction process, so that the harm to the environment is reduced.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating as well as a preparation method and application thereof.
Background
As an important component of modern materials, metals and alloys thereof are widely applied in various aspects such as national defense, transportation, mechanical manufacturing, chemical engineering, daily life and the like. However, the metal material is easily corroded or aged by corrosive media such as water, air, chloride ions and the like in the surrounding environment, so that the structure and performance of the metal material are lost. The metal corrosion not only brings loss to national economic development, but also brings hidden troubles to the life health and property safety of people. The most effective and simple method for protecting metals is to apply an organic coating on the surface of the metal to isolate the corrosive medium from the metal substrate.
Graphene is the thinnest anticorrosive material in the world at present, and the research in the anticorrosive field attracts the attention of researchers in various countries in the world. The graphene and the derivatives thereof have excellent barrier property, ultra-large specific surface area, good conductivity, high chemical stability and other properties, and have obvious improvement effects on the comprehensive properties of the anticorrosive coating, such as enhancing the corrosion resistance and wear resistance of the coating, improving the adhesive force of the coating to a base material, and simultaneously having the characteristics of environmental protection, safety, no secondary pollution and the like.
In the prior art, chinese patent application with publication number CN110240851A discloses a graphene epoxy glass flake coating and a preparation method thereof, which comprises a component a and a component B, wherein the component a comprises graphene, epoxy resin, an anti-settling agent, titanium dioxide, glass flakes, a dispersing agent, a filler and a first solvent, and the component B comprises a curing agent, an adhesion promoter and a second solvent.
The Chinese patent application with the publication number of CN109207022A discloses an epoxy glass flake anticorrosive paint and a preparation method and application thereof, and the epoxy glass flake anticorrosive paint comprises a component A and a component B, wherein the component A comprises epoxy resin, glass flakes, pigment, a dispersing agent, a silane coupling agent, a defoaming agent, an auxiliary agent and a solvent, and the component B comprises graphene slurry, nano calcium carbonate, cocoyl diethanol amine and aluminium tripolyphosphate.
However, in the prior art, a large amount of organic solvent and auxiliary agent are added in the preparation process, which is not beneficial to environmental protection, and the product is divided into A, B components, so that incompatibility phenomenon is easy to occur among materials in A, B components, thereby affecting the anticorrosion effect.
Disclosure of Invention
According to a first aspect of the invention, a graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating is provided, which is prepared from the following raw materials in parts by weight: 30-49 parts of epoxy resin, 3-6 parts of diisocyanate, 9-20 parts of unsaturated monobasic acid, 2-5 parts of acrylate monomer, 2-5 parts of dibasic acid or dibasic anhydride, 0.01-0.3 part of graphene oxide or modified graphene oxide, 30-40 parts of active diluent, 0.1-1 part of first catalyst, 0.1-1 part of second catalyst and 0.01-0.1 part of polymerization inhibitor.
In some embodiments, the modified graphene oxide is obtained by modifying graphene oxide with a silane coupling agent.
In some embodiments, the modified graphene oxide is prepared by the following method: uniformly mixing absolute ethyl alcohol, deionized water and tetraethyl silicate, stirring for 2-4h, then adding graphene oxide, performing ultrasonic treatment for 60-120min, then adding a silane coupling agent, stirring for 2-3h, and performing reflux reaction at 65-75 ℃ for 3-5h to obtain the modified graphene oxide.
In some embodiments, the silane coupling agent is selected from one or more of 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, tetraethyl silicate.
In some embodiments, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin with an epoxy equivalent weight of 230-340 g/mol; the diisocyanate is one or more selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
In some embodiments, the unsaturated monoacid is selected from one or more of acrylic acid, methacrylic acid, crotonic acid; the acrylate monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate; the dibasic acid or the dibasic acid anhydride is selected from one or more of fumaric acid, maleic anhydride and phthalic anhydride.
In some embodiments, the first catalyst is selected from dibutyltin dilaurate and the second catalyst is selected from one or more of benzyltriethylammonium chloride, benzyldiamine, triethylamine, diethylamine, triphenylphosphine.
In some embodiments, the polymerization inhibitor is selected from one or more of hydroquinone, p-tert-butylcatechol, catechol; the active diluent is selected from one or more of styrene, alpha-methyl styrene and methyl acrylate.
According to another aspect of the present invention, there is provided a preparation method of the graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating, the preparation method comprises: reacting diisocyanate and an acrylate monomer at 30-50 ℃ for 2-3h, adding epoxy resin, unsaturated monoacid, a polymerization inhibitor, graphene oxide or modified graphene oxide and a first catalyst, heating to 60-80 ℃ for reaction for 2-4h, adding dibasic acid or dibasic acid anhydride and a second catalyst, uniformly stirring, heating to 100-120 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 70-90 ℃, adding a reactive diluent, and mixing to obtain the modified graphene oxide.
According to the invention, firstly, half-blocking reaction of diisocyanate is carried out by using an acrylate monomer, then epoxy resin and unsaturated monoacid serving as a diluent are added, grafting reaction is carried out on isocyanate and hydroxyl on the epoxy resin, graphene oxide and dicarboxylic acid are added after the reaction is completed, functional groups on the graphene oxide participate in the reaction, and finally, blocking is carried out on the epoxy resin by using carboxylic acid, so that the graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating is obtained.
According to still another aspect of the invention, the application of the graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating in preparing a marine anticorrosive coating is provided. In particular to a heavy anti-corrosion coating for the surface of steel structures or concrete, such as marine engineering facilities such as offshore platforms, ship oil pipelines, large pressure steel pipes of hydropower stations, wharf steel piles, bridges, gates, ballast water tanks, gas pipes, sewage treatment pools, buried pipelines and the like.
Has the advantages that:
the graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating has excellent barrier property, better corrosion resistance and excellent mechanical property, and no organic solvent is added in the reaction process, so that the harm to the environment is reduced.
According to the invention, the multi-component hyperbranched reaction is carried out on diisocyanate, acrylate monomer, graphene oxide and epoxy resin, so that the crosslinking density of the resin and the dispersibility of the graphene oxide in the resin are increased.
The invention adopts reactant unsaturated monoacid as diluent, thereby avoiding the use of volatile solvent, not only reducing the harm to the environment, but also accelerating the total reaction rate and improving the utilization rate of raw materials.
The anticorrosive coating disclosed by the invention is simple in preparation process and has excellent barrier property, low surface energy and better corrosion resistance.
Drawings
FIG. 1 is a Tafel plot of tinplate coated with different coatings at a coating thickness of 25 μm in the experiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The starting materials referred to in the following examples are commercially available.
Example 1
The preparation method of the graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating comprises the following steps:
6.44g of toluene diisocyanate and hydroquinone serving as a polymerization inhibitor accounting for 0.05 percent of the total mass of the raw materials are put into a three-neck flask with a mechanical stirrer and a constant-pressure separating funnel, nitrogen is introduced, the temperature is raised to 45 ℃, 4.30g of hydroxyethyl acrylate is slowly dripped while stirring, and the reaction is carried out for about 2.5 hours under the protection of nitrogen until the mass percentage of the isocyanate is reduced to half of the initial value. Then, 50.00g of bisphenol A type epoxy resin E-44 (epoxy equivalent 227.27), 13.32g of acrylic acid, 0.06g of dibutyltin dilaurate and 0.02% of graphite oxide were added to a three-necked flask, and the mixture was stirred uniformly, heated to 70 ℃ and reacted for 3.5 hours. Then adding a catalyst benzyltriethylammonium chloride which is 0.6 percent of the total mass of the raw materials and 3.68g of fumaric acid, uniformly stirring, heating to 110 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 80 ℃, and finally adding 33.43g of active diluent styrene until the mixture is uniformly mixed to obtain the graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating.
Example 2
The preparation method of the graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating comprises the following steps:
6.44g of toluene diisocyanate and hydroquinone serving as a polymerization inhibitor accounting for 0.05 percent of the total mass of the raw materials are put into a three-neck flask with a mechanical stirrer and a constant-pressure separating funnel, nitrogen is introduced, the temperature is raised to 45 ℃, 4.30g of hydroxyethyl acrylate is slowly dripped while stirring, and the reaction is carried out for about 2.5 hours under the protection of nitrogen until the mass percentage of the isocyanate is reduced to half of the initial value. Then 50.00g of bisphenol A epoxy resin E-44 (epoxy equivalent weight 227.27), 13.32g of acrylic acid, 0.06g of dibutyltin dilaurate and graphene oxide accounting for 0.04 percent of the total mass of the raw materials are added into a three-neck flask, the mixture is uniformly stirred, the temperature is raised to 70 ℃, and the reaction is carried out for 3.5 hours. Then adding a catalyst benzyltriethylammonium chloride which is 0.6 percent of the total mass of the raw materials and 3.68g of fumaric acid, uniformly stirring, heating to 110 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 80 ℃, and finally adding 33.43g of active diluent styrene until the mixture is uniformly mixed to obtain the graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating.
Example 3
The preparation method of the modified graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating of the embodiment comprises the following steps:
(1) 160mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of tetraethyl orthosilicate are uniformly mixed, stirred for 3h at room temperature, then 0.1g of graphene oxide is added, ultrasonic treatment is carried out for 45min, then 2mL of 3-methacryloxypropyl trimethoxysilane and 2mL of 3-glycidoxypropyl trimethoxysilane are added, stirred for 3h at room temperature, then the mixture is transferred into an oil bath kettle for reflux reaction at 70 ℃ for 4h, and discharging, washing with an ethanol water solution and drying are carried out, thus obtaining the modified graphene oxide.
(2) 6.44g of toluene diisocyanate and hydroquinone serving as a polymerization inhibitor with the total mass of 0.028 percent of the raw material are put into a three-neck flask with a mechanical stirrer and a constant-pressure separating funnel, nitrogen is introduced, the temperature is raised to 45 ℃, 4.30g of hydroxyethyl acrylate is slowly dripped while stirring, and the reaction lasts for about 2.5 hours under the protection of nitrogen until the mass percent of the isocyanate is reduced to half of the initial value. Then 50.00g of bisphenol A epoxy resin E-44 (epoxy equivalent weight 227.27), 13.32g of acrylic acid, 0.06g of dibutyltin dilaurate and modified graphene oxide accounting for 0.03 percent of the total mass of the raw materials are added into a three-neck flask, the mixture is uniformly stirred, the temperature is raised to 70 ℃, and the reaction is carried out for 3.5 hours. Then adding a catalyst benzyltriethylammonium chloride accounting for 0.6 percent of the total mass of the raw materials and 3.68g of fumaric acid, uniformly stirring, heating to 110 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 80 ℃, and finally adding 33.43g of active diluent styrene until the mixture is uniformly mixed to obtain the modified graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating.
Example 4
The preparation method of the modified graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating of the embodiment comprises the following steps:
(1) 160mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of tetraethyl orthosilicate are uniformly mixed, stirred for 3h at room temperature, then 0.1g of graphene oxide is added, ultrasonic treatment is carried out for 45min, then 2mL of 3-methacryloxypropyl trimethoxysilane and 2mL of 3-glycidoxypropyl trimethoxysilane are added, stirred for 3h at room temperature, then the mixture is transferred into an oil bath kettle for reflux reaction at 70 ℃ for 4h, and discharging, washing with an ethanol water solution and drying are carried out, thus obtaining the modified graphene oxide.
(2) 6.44g of toluene diisocyanate and hydroquinone serving as a polymerization inhibitor accounting for 0.05 percent of the total mass of the raw materials are put into a three-neck flask with a mechanical stirrer and a constant-pressure separating funnel, nitrogen is introduced, the temperature is raised to 45 ℃, 4.30g of hydroxyethyl acrylate is slowly dripped while stirring, and the reaction is carried out for about 2.5 hours under the protection of nitrogen until the mass percentage of the isocyanate is reduced to half of the initial value. Then 50.00g of bisphenol A epoxy resin E-44 (epoxy equivalent weight 227.27), 13.32g of acrylic acid, 0.06g of dibutyltin dilaurate and modified graphene oxide accounting for 0.05% of the total mass of the raw materials are added into a three-neck flask, the mixture is uniformly stirred, the temperature is raised to 70 ℃, and the reaction is carried out for 3.5 hours. Then adding a catalyst benzyltriethylammonium chloride accounting for 0.6 percent of the total mass of the raw materials and 3.68g of fumaric acid, uniformly stirring, heating to 110 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 80 ℃, and finally adding 33.43g of active diluent styrene until the mixture is uniformly mixed to obtain the modified graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating.
Example 5
The preparation method of the modified graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating of the embodiment comprises the following steps:
(1) 160mL of absolute ethyl alcohol, 30mL of deionized water and 10mL of tetraethyl orthosilicate are uniformly mixed, stirred for 3h at room temperature, then 0.1g of graphene oxide is added, ultrasonic treatment is carried out for 45min, then 2mL of 3-methacryloxypropyl trimethoxysilane and 2mL of 3-glycidoxypropyl trimethoxysilane are added, stirred for 3h at room temperature, then the mixture is transferred into an oil bath kettle for reflux reaction at 70 ℃ for 4h, and discharging, washing with an ethanol water solution and drying are carried out, thus obtaining the modified graphene oxide.
(2) 6.44g of toluene diisocyanate and hydroquinone serving as a polymerization inhibitor accounting for 0.05 percent of the total mass of the raw materials are put into a three-neck flask with a mechanical stirrer and a constant-pressure separating funnel, nitrogen is introduced, the temperature is raised to 45 ℃, 4.30g of hydroxyethyl acrylate is slowly dripped while stirring, and the reaction is carried out for about 2.5 hours under the protection of nitrogen until the mass percentage of the isocyanate is reduced to half of the initial value. Then 50.00g of bisphenol A epoxy resin E-44 (epoxy equivalent weight 227.27), 14.50g of acrylic acid, 0.06g of dibutyltin dilaurate and modified graphene oxide accounting for 0.03 percent of the total mass of the raw materials are added into a three-neck flask, the mixture is uniformly stirred, the temperature is raised to 70 ℃, and the reaction is carried out for 3.5 hours. Then adding a catalyst benzyltriethylammonium chloride accounting for 0.6 percent of the total mass of the raw materials and 2.26g of maleic anhydride, uniformly stirring, heating to 110 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 80 ℃, and finally adding 33.43g of active diluent styrene until the mixture is uniformly mixed to obtain the modified graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating.
Comparative example 1
Epoxy glass flake coatings (IPN8710, produced by Jiasheng coatings of Cangzhou, using epoxy resin as the main base material and glass flakes as the filler).
Next, the graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating prepared in examples 1 to 2, the modified graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating prepared in examples 3 to 5, and the epoxy glass flake coating of comparative example 1 were coated on polished tinplate, and the corrosion resistance and mechanical properties were tested by the following test methods:
1. chemical corrosion resistance test: and respectively soaking the cured film coated on the polished tinplate in a 10% NaOH solution, a 10% HCl solution and a 3.5% NaCl solution for 15 days, taking out the cured film, and observing whether the cured film has the phenomena of bubbling, rusting, falling off and the like.
2. Salt spray resistance test: and (3) performing a salt spray resistance test on the curing film coated on the polished tinplate by using a BGD 880/S salt spray corrosion test box.
3. Tensile strength and fracture growth rate: and (3) testing the mechanical property of the casting body of the cured film coated on the polished tinplate according to the national standard GB/T1040.3-2006.
The test results are shown in table 1.
TABLE 1 paint Performance test results
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Tolerance of 10%NaOHSolution/15 d | Is free of | Is free of | Is free of | Is free of | Is free of | Foaming |
| Tolerance of 10%HClSolution/15 d | Is free of | Is free of | Is free of | Is free of | Is free of | Foaming |
| 3.5 percent of the total weightNaClSolution/15 d | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of |
| Salt spray resistance per 1000h | Is free of | Is free of | Is free of | Is free of | Is free of | Rust formation |
| Tensile strength-MPa | 79.44 | 81.29 | 88.73 | 87.76 | 85.25 | 70.11 |
| Percentage of growth at break/%) | 14.49 | 13.27 | 16.63 | 14.45 | 15.54 | 9.6 |
Note: "none" in Table 1 means no blistering, rusting, flaking, etc.
As can be seen from table 1, compared with the epoxy glass flake coating of comparative example 1, the graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating and the modified graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating of the present invention have better corrosion resistance to corrosive media such as acid, alkali, water, air, and chloride ions, and better mechanical properties.
Then, in order to further detect the corrosion resistance of the composite coating of the present invention, the graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating prepared in example 1, the modified graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coatings prepared in examples 3 to 4, and the epoxy glass flake coating of comparative example 1 were coated on polished tinplate to a coating thickness of 25 μm, and the corrosion rate of tinplate was determined by tafel curve.
The test method specifically comprises the following steps: the corrosion resistance of the metal coating is characterized by a testing method of a potentiodynamic polarization curve by using a CHI660E electrochemical workstation, a three-electrode electrolytic cell system is used in the test, a tinplate is used as a working electrode, a platinum electrode is used as a counter electrode, an Ag/AgCl system is used as a reference electrode, and a 3.5 wt% sodium chloride aqueous solution is used as an electrolyte medium. The coating was applied to the working electrode in a 1cm x 1cm format and tested at open circuit potential.
The results of the detection are shown in FIG. 1. As can be seen from fig. 1, the corrosion current (Icorr) of the tinplate coated with the composite coating of the present invention is significantly lower and the corrosion potential (Ecorr) is significantly increased than that of the tinplate coated with the coating of comparative example 1, thereby indicating that the composite coating of the present invention has better corrosion resistance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The graphene oxide/epoxy vinyl ester resin heavy-duty anticorrosive solvent-free composite coating is characterized by being prepared from the following raw materials in parts by weight: 30-49 parts of epoxy resin, 3-6 parts of diisocyanate, 9-20 parts of unsaturated monobasic acid, 2-5 parts of acrylate monomer, 2-5 parts of dibasic acid or dibasic anhydride, 0.01-0.3 part of graphene oxide or modified graphene oxide, 30-40 parts of active diluent, 0.1-1 part of first catalyst, 0.1-1 part of second catalyst and 0.01-0.1 part of polymerization inhibitor.
2. The graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating according to claim 1, wherein the modified graphene oxide is obtained by modifying graphene oxide with a silane coupling agent.
3. The graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating according to claim 2, wherein the modified graphene oxide is prepared by the following method: mixing absolute ethyl alcohol, deionized water and tetraethyl silicate, stirring for 2-4h, then adding graphene oxide, performing ultrasonic treatment for 60-120min, then adding a silane coupling agent, stirring for 2-3h, and performing reflux reaction at 65-75 ℃ for 3-5h to obtain the modified graphene oxide.
4. The graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating according to claim 2 or 3, wherein the silane coupling agent is selected from one or more of 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, and tetraethyl silicate.
5. The graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating as claimed in claim 1, wherein the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin with an epoxy equivalent of 230-340 g/mol; the diisocyanate is selected from one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
6. The graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating according to claim 1, wherein the unsaturated monobasic acid is selected from one or more of acrylic acid, methacrylic acid and crotonic acid; the acrylate monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate; the dibasic acid or the dibasic acid anhydride is selected from one or more of fumaric acid, maleic anhydride and phthalic anhydride.
7. The graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating according to claim 1, wherein the first catalyst is selected from dibutyltin dilaurate, and the second catalyst is selected from one or more of benzyltriethylammonium chloride, benzyldiamine, triethylamine, diethylamine, and triphenylphosphine.
8. The graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating according to claim 1, wherein the polymerization inhibitor is one or more selected from hydroquinone, p-tert-butylcatechol, and catechol; the reactive diluent is selected from one or more of styrene, alpha-methyl styrene and methyl acrylate.
9. The preparation method of the graphene oxide/epoxy vinyl ester resin heavy-duty solvent-free composite coating according to any one of claims 1 to 8, characterized in that the preparation method comprises the following steps: reacting diisocyanate and an acrylate monomer at 30-50 ℃ for 2-3h, adding epoxy resin, unsaturated monoacid, a polymerization inhibitor, graphene oxide or modified graphene oxide and a first catalyst, heating to 60-80 ℃ for reaction for 2-4h, adding dibasic acid or dibasic acid anhydride and a second catalyst, uniformly stirring, heating to 100-120 ℃ for reaction until the acid value is reduced to below 8mgKOH/g, cooling to 70-90 ℃, adding a reactive diluent, and mixing to obtain the modified graphene oxide.
10. Use of the graphene oxide/epoxy vinyl ester resin heavy duty solvent-free composite coating according to any one of claims 1 to 8 in the preparation of marine anticorrosive coatings.
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