Graphene oxide filler, anticorrosive coating and preparation method and application thereof

Abstract

This invention discloses a graphene oxide filler, an anti-corrosion coating, its preparation method, and its application, relating to the field of functional filler technology. The raw materials for preparing the graphene oxide filler of this invention include esterified lignin, zinc-containing monomers, and graphene oxide; the mass ratio of graphene oxide to esterified lignin is 1:(0.05-30); the mass ratio of graphene oxide to zinc-containing monomers is 1:(0.05-50). This graphene oxide filler exhibits excellent anti-corrosion performance and also possesses photothermal conversion capabilities. When used in coatings, it has self-healing functions and good dispersibility and compatibility in resin systems. It is suitable for preparing anti-corrosion coatings, forming anti-corrosion coatings, and is particularly suitable for preparing anti-corrosion coatings for equipment, instruments, ships, household goods, decorations, or engineering buildings, extending the service life of metal products.

Description

Technical Field

[0001] This invention relates to the field of functional filler technology, and in particular to a graphene oxide filler, an anti-corrosion coating, its preparation method and application. Background Technology

[0002] In industrial production, most metals and their alloys are susceptible to corrosion from solvents or moisture in the environment. This corrosion can lead to deterioration of the metal's properties and even material failure. Anti-corrosion coatings can isolate the underlying metal from corrosive media, thereby reducing the risk of corrosion. However, currently used coatings lack sufficient corrosion resistance and cannot provide long-term protection for metal materials. Using functional nanofillers to improve the anti-corrosion performance of coatings is a relatively effective composite approach. However, the raw materials currently used to improve nanofillers are mostly non-renewable materials, which are highly harmful to the environment and lack long-term anti-corrosion capabilities. On the other hand, unmodified nanofillers, due to structural limitations, lack corresponding anti-corrosion functions and cannot improve the anti-corrosion performance of coatings. Summary of the Invention

[0003] The present invention aims to at least solve one of the aforementioned technical problems existing in the prior art. Therefore, the object of the present invention is to provide a graphene oxide filler that modifies graphene oxide using esterified lignin and zinc-containing monomers, thereby enhancing the photothermal conversion capability of the graphene oxide filler, endowing it with self-healing function, and improving its corrosion resistance.

[0004] A second aspect of the present invention provides a method for preparing graphene oxide filler.

[0005] A third aspect of the present invention provides an anti-corrosion coating.

[0006] A fourth aspect of the present invention provides a method for preparing an anti-corrosion coating.

[0007] The fifth aspect of the present invention provides an application of an anti-corrosion coating.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides a graphene oxide filler, the raw materials for which include esterified lignin, zinc-containing monomers and graphene oxide;

[0010] The mass ratio of graphene oxide to esterified lignin is 1:(0.05-30); the mass ratio of graphene oxide to zinc-containing monomer is 1:(0.05-50).

[0011] The graphene oxide filler of the present invention uses esterified lignin, zinc-containing monomers and graphene oxide as raw materials. The graphene oxide is modified by zinc-containing monomers and esterified lignin to obtain a graphene oxide filler with excellent anti-corrosion properties. Furthermore, the graphene oxide filler can form a good dispersion in the resin system and has good compatibility.

[0012] Lignin is widely available, environmentally friendly, renewable, and carbon-neutral. Using it as a modifier for graphene oxide not only solves the problems of poor dispersibility and compatibility of graphene oxide in coating resin systems but also increases the added value of biomass materials. The modification of esterified lignin not only affects the anti-corrosion performance of graphene oxide fillers but also influences their dispersibility, compatibility, and interfacial interactions in resin systems, thus improving the anti-corrosion effect of coatings containing this graphene oxide filler.

[0013] Zinc-containing monomers refer to compounds containing zinc, which are widely available, inexpensive, and possess excellent anti-corrosion properties. When used as self-healing agents, they can endow graphene oxide fillers with self-healing properties. This self-healing property mainly refers to the ability of zinc ions to react with hydroxyl ions generated during corrosion to form a zinc hydroxide protective film, preventing further corrosion. Simultaneously, zinc-containing monomers can also enhance the photothermal conversion ability of graphene oxide fillers. These self-healing and photothermal conversion properties further improve the anti-corrosion performance of graphene oxide, extending product lifespan when used in coatings. Furthermore, zinc-containing monomers also affect the dispersibility, compatibility, and interfacial interactions of graphene oxide fillers in resin systems.

[0014] In this invention, in order to ensure the modification effect of esterified lignin and zinc-containing monomers on graphene oxide, effectively improve the self-healing and photothermal conversion properties of graphene oxide filler, and enhance its anti-corrosion properties, the mass ratio of esterified lignin and zinc-containing monomers to graphene oxide in the raw materials is controlled within a suitable range. Too high or too low amounts of esterified lignin and zinc-containing monomers are not conducive to improving anti-corrosion and self-healing properties.

[0015] Preferably, the mass ratio of the graphene oxide to the esterified lignin is 1:(0.5-10).

[0016] More preferably, the mass ratio of the graphene oxide to the esterified lignin is 1:(1-5).

[0017] More preferably, the mass ratio of the graphene oxide to the esterified lignin is 1:(1-3).

[0018] Preferably, the mass ratio of the graphene oxide to the zinc-containing monomer is 1:(0.1-10).

[0019] More preferably, the mass ratio of the graphene oxide to the zinc-containing monomer is 1:(0.5-3).

[0020] More preferably, the mass ratio of the graphene oxide to the zinc-containing monomer is 1:(1-2).

[0021] Preferably, the zinc-containing monomer includes at least one of zinc nitrate, zinc stearate, and zinc sulfate.

[0022] Preferably, the esterified lignin is prepared by a method comprising the following steps: mixing lignin with an acyl chloride monomer and reacting to obtain esterified lignin; wherein the acyl chloride monomer comprises at least one of acetyl chloride, benzoyl chloride, propionyl chloride, dodecyl chloride, furfural chloride, myristoyl chloride, heptanyl chloride, and stearoyl chloride.

[0023] More preferably, the reaction is carried out at room temperature.

[0024] Acyl chloride monomers have high reactivity and can undergo esterification reactions with hydroxyl groups on lignin at room temperature or low temperature to obtain the desired esterified lignin.

[0025] More preferably, the reaction time is 24–120 h.

[0026] More preferably, the reaction time is 45 to 50 hours.

[0027] More preferably, the mixing method of the lignin and acyl chloride monomer includes ultrasound; the ultrasound time is 10-60 min.

[0028] More preferably, the lignin includes at least one of sodium lignin sulfonate, bamboo lignin, syringyl lignin, guaiacyl lignin, and p-hydroxyphenyl lignin.

[0029] More preferably, the lignin is first mixed with a neutralizing agent in an organic solvent, stabilized at a temperature of -5 to 5°C, and then mixed with an acyl chloride monomer.

[0030] More preferably, the stabilization time is 5 to 20 minutes.

[0031] More preferably, the neutralizing agent includes at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and sodium carbonate.

[0032] More preferably, the organic solvent includes at least one of tetrahydrofuran, chloroform, toluene, N,N-dimethylformamide, acetone, and butanone.

[0033] More preferably, after the reaction, the pH of the system is adjusted to 2-3.

[0034] More preferably, the pH is adjusted using an acidic solution; the acidic solution includes at least one of hydrochloric acid, nitric acid, and sulfuric acid.

[0035] A second aspect of the present invention provides a method for preparing the graphene oxide filler described in the first aspect of the present invention, comprising the following steps:

[0036] Graphene oxide and esterified lignin were mixed and dissolved, and after the first reaction, solid-liquid separation was performed to obtain solid A, which was then dried to obtain graphene oxide filler precursor.

[0037] The graphene oxide filler precursor is mixed with a zinc-containing monomer, and after a second reaction, solid-liquid separation is performed to obtain solid B, which is then dried to obtain the graphene oxide filler.

[0038] The graphene oxide filler precursor obtained after esterification lignin grafting exhibits electronegativity. Zinc ions from zinc monomers can be loaded onto graphene oxide through electrostatic adsorption to obtain the desired graphene oxide filler.

[0039] Preferably, the temperature of the first reaction is 100–200°C.

[0040] More preferably, the temperature of the first reaction is 130–170°C.

[0041] More preferably, the temperature of the first reaction is 140–160°C.

[0042] Preferably, the reaction time for the first reaction is 2 to 48 hours.

[0043] More preferably, the reaction time of the first reaction is 2 to 10 hours.

[0044] More preferably, the first reaction takes 3 to 6 hours.

[0045] Preferably, the second reaction is carried out under conditions of pH 8 to 12.

[0046] More preferably, the second reaction is carried out under conditions of pH 8 to 10.

[0047] More preferably, the second reaction is carried out at a pH of 8 to 9.

[0048] More preferably, the pH of the second reaction is adjusted using an alkaline reagent.

[0049] More preferably, the alkaline reagent includes one of sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.

[0050] More preferably, the graphene oxide filler precursor is uniformly dispersed in water, and then a zinc-containing monomer is added to adjust the reaction pH.

[0051] More preferably, the method of uniform dispersion includes ultrasound.

[0052] It should be understood that in this invention, the role of ultrasonic treatment is to disperse and mix the system evenly without affecting the structure and properties of the material.

[0053] Preferably, the temperature of the second reaction is 50–80°C.

[0054] More preferably, the temperature of the second reaction is 50–70°C.

[0055] Preferably, the second reaction takes 30 to 200 minutes.

[0056] More preferably, the second reaction time is 100-150 min.

[0057] Preferably, the solid-liquid separation method includes centrifugation; the centrifugation is followed by a washing step.

[0058] Preferably, a catalyst is added when the graphene oxide is mixed with the esterified lignin; the organic solvent used for the mixing and dissolution includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, toluene, butanone, anhydrous ethanol, and dimethyl sulfoxide.

[0059] More preferably, the catalyst comprises at least one selected from 4-dimethylaminopyridine, triethylamine, 2-methylimidazole, boron trifluoride, benzyldimethylamine, and 2-ethyl-4-methylimidazole.

[0060] More preferably, the amount of the catalyst is 1 to 10% of the mass of graphene oxide.

[0061] More preferably, the amount of the catalyst is 2 to 8% of the mass of graphene oxide.

[0062] More preferably, the amount of catalyst used is 3-6% of the mass of graphene oxide.

[0063] A third aspect of the present invention provides an anti-corrosion coating comprising the graphene oxide filler described in the first aspect of the present invention, or the graphene oxide filler prepared by the preparation method described in the second aspect of the present invention.

[0064] Preferably, the anti-corrosion coating further includes epoxy vinyl ester resin, solvent and additives; the graphene oxide filler in the anti-corrosion coating has a mass percentage of 0.05-2%.

[0065] More preferably, the graphene oxide filler in the anti-corrosion coating has a mass percentage of 0.05% to 1%.

[0066] More preferably, the graphene oxide filler in the anti-corrosion coating has a mass percentage of 0.1% to 0.5%.

[0067] Preferably, the anti-corrosion coating comprises, by mass percentage, the following components: 50-90% epoxy vinyl ester resin, 0.05-2% graphene oxide filler, 0.01-3% additives, and the balance being solvent.

[0068] More preferably, the anti-corrosion coating comprises, by weight percentage, the following components: 60-80% epoxy vinyl ester resin, 0.1-0.5% graphene oxide filler, 1-2% additives, and the balance being solvent.

[0069] Preferably, the raw materials for preparing the epoxy vinyl ester resin include epoxy resin, hydroquinone, benzyltriethylammonium chloride, and acrylic acid.

[0070] Preferably, the solvent includes styrene.

[0071] Preferably, the additives include cobalt naphthenate and / or 2-butanone peroxide.

[0072] A fourth aspect of the present invention provides a method for preparing the anti-corrosion coating described in the third aspect of the present invention, comprising the following steps:

[0073] The components are mixed to obtain the anti-corrosion coating.

[0074] In this invention, graphene oxide filler can be well dispersed in epoxy vinyl ester resin through simple mixing.

[0075] Preferably, the mixing method includes ultrasound.

[0076] The fifth aspect of the present invention provides the application of the anti-corrosion coating described in the third aspect of the present invention in the preparation of anti-corrosion coatings.

[0077] Preferably, the anti-corrosion coating includes anti-corrosion coatings for equipment and instruments, ships, household goods, decorations, or engineering construction materials.

[0078] Preferably, the curing temperature of the coating is 90–200°C.

[0079] More preferably, the curing conditions for the coating are to cure it sequentially at temperatures of 90–110°C, 120–140°C, 150–170°C, and 175–190°C for 1–3 h, 1–2 h, 1–4 h, and 1–4 h, respectively.

[0080] Compared with the prior art, the beneficial effects of the present invention are:

[0081] (1) This invention uses molecular structure design and composite reinforcement strategy to prepare graphene oxide filler with esterified lignin and zinc-containing monomers as modifiers. By controlling the dosage range of esterified lignin and zinc-containing monomers, the anti-corrosion performance of graphene oxide filler is effectively improved, and it is endowed with photothermal conversion ability and self-healing performance. This solves the problems of poor dispersibility and poor compatibility of graphene oxide filler in resin system. Moreover, the raw material lignin used is a renewable and environmentally friendly raw material. While solving the problem that the modifiers of the anti-corrosion functional fillers used in existing coatings are harmful to the environment, this invention improves the application effect of graphene oxide filler and enhances the anti-corrosion effect of coatings containing graphene oxide filler.

[0082] (2) The anti-corrosion coating of the present invention contains specific graphene oxide filler. When the anti-corrosion coating forms a coating, the "maze effect", dense three-dimensional network structure and self-healing anti-corrosion performance formed by the graphene oxide filler have a synergistic anti-corrosion effect, thereby improving the anti-corrosion performance of the anti-corrosion coating and enhancing the photothermal conversion capability of the coating.

[0083] (3) The preparation process of the graphene oxide filler and anti-corrosion coating of the present invention is simple, convenient to operate, and the raw materials are readily available and easy to implement.

[0084] (4) The anti-corrosion coating of the present invention contains graphene oxide filler, and the coating formed therefrom has excellent anti-corrosion effect and also has photothermal conversion performance. Furthermore, the self-healing property of zinc ions in the graphene oxide filler enables it to generate a layer of zinc hydroxide protective film on the surface when metal is corroded and generates hydroxide ions, thereby achieving a self-healing anti-corrosion effect and significantly improving the anti-corrosion ability of the coating. It is suitable for preparing anti-corrosion coatings for equipment, instruments, ships, household goods, decorations or engineering buildings, and extending the service life of metal products. Attached Figure Description

[0085] Figure 1 The reaction route diagram for preparing the anti-corrosion coating in the embodiments of the present invention is shown.

[0086] Figure 2 The infrared spectrum of the esterified lignin used in Example 1 of this invention is shown.

[0087] Figure 3 This is the XPS spectrum of the graphene oxide filler in Example 1 of the present invention.

[0088] Figure 4 This is a Bode diagram of the coating formed by the paint of Comparative Example 1 of the present invention.

[0089] Figure 5 This is a Bode diagram of the coating formed by the anti-corrosion coating of Embodiment 2 of the present invention.

[0090] Figure 6This is a Bode diagram of the coating formed by the anti-corrosion coating of Embodiment 3 of the present invention.

[0091] Figure 7 This is a Bode diagram of the coating formed by the anti-corrosion coating of Embodiment 4 of the present invention.

[0092] Figure 8 The temperature curves of the coatings in Examples 2-4 and Comparative Example 1 of the present invention within 180s are shown. Detailed Implementation

[0093] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0094] In the following examples and comparative examples, the preparation method of esterified lignin is as follows: 5g of lignin is dissolved in 100mL of tetrahydrofuran, and 11.4mL of triethylamine is added; then, the mixture is transferred to an ice-water bath (-5 to 5℃) and stabilized for 10min; then, 8.5mL of acetyl chloride solution dissolved in 20.0mL of tetrahydrofuran is slowly added dropwise to the mixture, and stirred at room temperature for 48h; after the reaction, the pH of the mixture is adjusted to 2 with 1mol / L hydrochloric acid solution, poured into 1000mL of deionized water, and stirred for 30min; the solution is filtered, washed three times with deionized water, and the resulting filter cake is dried in a vacuum oven at 55℃ to obtain esterified lignin.

[0095] In the following examples and comparative examples, the epoxy vinyl ester resin was prepared as follows: 20.0 g of epoxy resin E44, 0.02 wt% of hydroquinone and 0.5 wt% of benzyltriethylammonium chloride were added to a 250 mL flask and stirred; when the temperature reached 90 °C, 6.661 g of acrylic acid was slowly added dropwise to the flask; the temperature was raised to 110 °C and the reaction was continued for 3.5 h to obtain the epoxy vinyl ester resin.

[0096] The following detailed description is provided with reference to specific embodiments and comparative examples:

[0097] Example 1

[0098] This embodiment provides a graphene oxide filler, the preparation method of which includes the following steps:

[0099] The preparation method of graphene oxide filler is as follows: 0.2 g of esterified lignin, 0.1 g of graphene oxide (GO, commercially available) and 0.005 g of 4-dimethylaminopyridine were added to a flask and dissolved in 50 mL of N,N-dimethylformamide. The mixture was stirred at 150 °C for 5 h and then centrifuged. The product was washed with N,N-dimethylformamide and anhydrous ethanol and dried to obtain lignin-modified GO. Next, 0.1 g of lignin-modified GO was dispersed in 50 mL of deionized water and ultrasonically dispersed for 10 min. Then, 0.15 g of Zn(NO3)2·6H2O was added, and the pH value was adjusted to 8 with NaOH (10 wt%) solution. The mixture was reacted at 60 °C for 2 h, centrifuged, washed and filtered. Finally, the product was dried at 60 °C for 24 h to obtain graphene oxide filler, which was denoted as Zn@LGO.

[0100] The Zn@LGO from Example 1 was used to prepare the anti-corrosion coatings of Examples 2-4. The reaction route diagrams for the preparation of the anti-corrosion coatings are shown below. Figure 1 As shown.

[0101] Example 2

[0102] This embodiment provides an anti-corrosion coating, which, by mass percentage, comprises 70% epoxy vinyl ester resin, 0.1% graphene oxide filler, 0.3% cobalt naphthenate, 1% 2-butanone peroxide, and the balance being styrene.

[0103] The preparation method of this anti-corrosion coating is as follows:

[0104] 3g of a styrene solution of 70wt% epoxy vinyl ester resin was added to a glass bottle, followed by the addition of 0.1wt% Zn@LGO, and ultrasonically dispersed. Subsequently, 0.3wt% cobalt naphthenate and 1.0wt% 2-butanone peroxide were added to the system, and the mixture was stirred until homogeneous to obtain the anti-corrosion coating.

[0105] Example 3

[0106] This embodiment provides an anti-corrosion coating, which, by mass percentage, comprises 70% epoxy vinyl ester resin, 0.2% graphene oxide filler, 0.3% cobalt naphthenate, 1% 2-butanone peroxide, and the balance being styrene.

[0107] The preparation method of this anti-corrosion coating is as follows:

[0108] 3g of a styrene solution of 70wt% epoxy vinyl ester resin was added to a glass bottle, followed by the addition of 0.2wt% Zn@LGO, and ultrasonically dispersed. Subsequently, 0.3wt% cobalt naphthenate and 1.0wt% 2-butanone peroxide were added to the system, and the mixture was stirred until homogeneous to obtain the anti-corrosion coating.

[0109] Example 4

[0110] This embodiment provides an anti-corrosion coating, which, by mass percentage, comprises 70% epoxy vinyl ester resin, 0.4% graphene oxide filler, 0.3% cobalt naphthenate, 1% 2-butanone peroxide, and the balance being styrene.

[0111] The preparation method of this anti-corrosion coating is as follows:

[0112] 3g of a styrene solution of 70wt% epoxy vinyl ester resin was added to a glass bottle, followed by the addition of 0.4wt% Zn@LGO, and ultrasonically dispersed. Subsequently, 0.3wt% cobalt naphthenate and 1.0wt% 2-butanone peroxide were added to the system, and the mixture was stirred until homogeneous to obtain the anti-corrosion coating.

[0113] Comparative Example 1

[0114] This comparative example provides a coating that, compared to Example 1, does not contain Zn@LGO, and is prepared by the following method:

[0115] Add 3g of 70wt% epoxy vinyl ester resin solution to a glass bottle, then add 0.3wt% cobalt naphthenate and 1.0wt% 2-butanone peroxide, mix well to obtain the anti-corrosion coating.

[0116] In order to verify the performance of the coating prepared by the anti-corrosion coating of the present invention, the coatings prepared in Examples 2 to 4 and Comparative Example 1 were cured into coatings and their performance was tested.

[0117] 1. Coating preparation

[0118] The coatings prepared in Examples 2-4 and Comparative Example 1 were applied to the surface of steel plates using a coater. The plates were first placed in an oven at 25°C overnight, and then each coated steel plate was sequentially cured at 100°C, 130°C, 160°C, and 180°C for 3 hours, 2 hours, 2 hours, and 2 hours, respectively, to obtain the coatings. The coatings obtained in Comparative Example 1 and Examples 2-4 were respectively designated as VER-0 (Comparative Example 1), VER-1 (Example 2), VER-2 (Example 3), and VER-3 (Example 4).

[0119] 2. Testing Methods

[0120] (1) Chemical structure characterization

[0121] Test method: The functional groups of the sample were characterized by Fourier transform infrared spectroscopy (FTIR, Nicolet iS10, Germany). The wavelength range of the test was 4000–500 cm⁻¹. -1 The number of scans was 32.

[0122] (2) XPS test

[0123] Test method: X-ray photoelectron spectroscopy (XPS, Thermo Scientific K Alpha) was used to characterize the elemental types on the sample surface.

[0124] (3) Electrochemical testing

[0125] Test Method: Electrochemical test data of the coating were obtained using an electrochemical workstation (CHI-660E). During the test, the corrosive medium was 3.5 wt% saline solution, with an Ag / AgCl electrode used as the reference electrode and a platinum plate as the counter electrode.

[0126] (4) Photothermal conversion performance

[0127] Test method: Near-infrared light source (1.0 W·cm) was used. -2 The photothermal conversion performance of the sample was evaluated using a FU980AD1200-GD22, and the temperature change of the sample was recorded at different irradiation times.

[0128] 3. Test Results

[0129] The performance test results of the coatings prepared from the anti-corrosion coatings of Examples 2-4 and the coating of Comparative Example 1 are shown in Table 1.

[0130] Table 1 Performance test results of the coating

[0131]

[0132] The following is combined Figures 2-8 Table 1 and Table 1 analyze the anti-corrosion coating and esterified lignin and graphene oxide filler of the present invention.

[0133] The structure of the esterified lignin used in Example 1 of this invention was characterized, and the results are as follows: Figure 2 As shown. From Figure 2 It can be found that at 3343cm -1 The characteristic peak at 1765 cm⁻¹ belongs to the hydroxyl peak on esterified lignin, indicating that esterified lignin contains a certain amount of hydroxyl groups. Meanwhile, at 1765 cm⁻¹... -1 There is a distinct characteristic peak that is attributed to the ester group on the esterified lignin, indicating that the esterified lignin was successfully prepared.

[0134] Figure 3 This is the XPS spectrum of the graphene oxide filler from Example 1 of the present invention. Figure 3 As can be seen, in addition to carbon and oxygen, zinc was also detected on the Zn@LGO surface, indicating that zinc ions were loaded onto GO.

[0135] contrast Figure 4 , Figure 5 , Figure 6 , Figure 7 As shown in Table 1, the coatings formed by the examples and comparative examples had similar impedance values ​​at the beginning of immersion. However, after immersion in salt water for 100 days, the impedance modulus of the coatings decreased, indicating a weakening of their anti-corrosion performance. Specifically, the modulus of the coating in Comparative Example 1 decreased to 5.0 × 10⁻⁶. 7 Ω·cm 2 This indicates that its corrosion resistance is poor. However, in Examples 2-4, the corrosion resistance of the coating was improved after adding Zn@LGO to the coating, and the decrease in impedance modulus was smaller. The impedance modulus of the coatings in Examples 2, 3, and 4 were 4.6 × 10⁻⁶. 8 Ω·cm 2 1.1×10 9 Ω·cm 2 and 1.3×10 9 Ω·cm 2 Among them, Example 4 yielded the coating with the highest impedance modulus, which was two orders of magnitude higher than the control example. This indicates that the anti-corrosion performance of the coating is enhanced with the increase of Zn@LGO content. It should be noted that, since the compatibility of the system and the dispersibility of Zn@LGO also need to be considered, a higher Zn@LGO content is not necessarily better.

[0136] Combination Figure 8 As shown in Table 1, the surface temperature of the coatings in the examples and comparative examples increased rapidly within seconds of near-infrared irradiation, but the surface temperature change was smaller after 50 seconds of irradiation. After 180 seconds of irradiation, the surface temperatures of the coatings in Comparative Example 1 and Examples 2, 3, and 4 were 81.9℃, 114.3℃, 122.1℃, and 139.2℃, respectively. This indicates that adding Zn@LGO to the resin coating can endow the coating with excellent photothermal conversion properties and self-healing properties, thereby further improving the anti-corrosion effect of the coating and enhancing its protective function.

[0137] In summary, the graphene oxide filler of this invention exhibits excellent anti-corrosion performance, while also possessing photothermal conversion capabilities. When used in coatings, it also demonstrates self-healing properties and good dispersibility and compatibility in resin systems. This graphene oxide filler is suitable for preparing anti-corrosion coatings. When the anti-corrosion coating forms a layer, the "maze effect," dense three-dimensional network structure, and self-healing function of the graphene oxide filler synergistically provide anti-corrosion protection, resulting in a coating with excellent anti-corrosion performance. Therefore, the anti-corrosion coating of this invention is suitable for preparing anti-corrosion coatings, especially for equipment, instruments, ships, household goods, decorations, or engineering structures, extending the service life of metal products.

[0138] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An anti-corrosion coating, characterized in that, The anti-corrosion coating includes graphene oxide filler; the raw materials for preparing the graphene oxide filler include esterified lignin, zinc-containing monomers, and graphene oxide. The mass ratio of graphene oxide to esterified lignin is 1:(1~3); the mass ratio of graphene oxide to zinc-containing monomer is 1:(0.1~10); both esterified lignin and zinc-containing monomer are used as modifiers to modify the graphene oxide. The graphene oxide filler in the anti-corrosion coating has a mass percentage of 0.1% to 2%. The zinc-containing monomer includes at least one of zinc nitrate, zinc stearate, and zinc sulfate; The esterified lignin is prepared by a method comprising the following steps: mixing lignin with an acyl chloride monomer and reacting to obtain esterified lignin; wherein the acyl chloride monomer comprises at least one of acetyl chloride, benzoyl chloride, propionyl chloride, dodecyl chloride, furfural chloride, myristoyl chloride, heptanyl chloride, and stearoyl chloride; The preparation method of the graphene oxide filler includes the following steps: Graphene oxide and esterified lignin were mixed and dissolved, and after the first reaction, solid-liquid separation was performed to obtain solid A, which was then dried to obtain graphene oxide filler precursor. The graphene oxide filler precursor is mixed with a zinc-containing monomer, and after a second reaction, solid-liquid separation is performed to obtain solid B, which is then dried to obtain the graphene oxide filler.

2. The anti-corrosion coating according to claim 1, characterized in that, The temperature of the first reaction is 100~200℃; And / or, the second reaction is carried out under conditions of pH 8 to 12; And / or, the temperature of the second reaction is 50~80℃.

3. The anti-corrosion coating according to claim 1, characterized in that, The anti-corrosion coating also includes epoxy vinyl ester resin, solvent, and additives.

4. The anti-corrosion coating according to claim 3, characterized in that, The anti-corrosion coating comprises, by mass percentage, the following components: 50-90% epoxy vinyl ester resin, 0.1-2% graphene oxide filler, 0.01-3% additives, and the balance being solvent.

5. The anti-corrosion coating according to claim 3, characterized in that, The solvent includes styrene; And / or, the adjuvants include cobalt naphthenate and / or 2-butanone peroxide.

6. A method for preparing the anti-corrosion coating according to any one of claims 1 to 5, characterized in that, Includes the following steps: The components are mixed to obtain the anti-corrosion coating.

7. The use of the anti-corrosion coating according to any one of claims 1 to 5 in the preparation of an anti-corrosion coating.

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