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

Abstract

The invention discloses a graphene oxide filler, an anti-corrosion coating as well as a preparation method and application of the anti-corrosion coating, and relates to the technical field of functional fillers. The graphene oxide filler is prepared from the following raw materials: esterified lignin, a zinc-containing monomer and graphene oxide, the mass ratio of the graphene oxide to the esterified lignin is 1: (0.05-30); the mass ratio of the graphene oxide to the zinc-containing monomer is 1: (0.05-50). The graphene oxide filler is excellent in corrosion resistance, has photo-thermal conversion capacity, has a self-repairing function when being used in the coating, is good in dispersity and compatibility in a resin system, is suitable for preparing the corrosion-resistant coating and forming the corrosion-resistant coating, and is particularly suitable for preparing the corrosion-resistant coating of equipment instruments, ships, household articles, ornaments or engineering buildings. And the service life of a metal product is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of functional fillers, and in particular to a graphene oxide filler, an anti-corrosion coating, and a preparation method and application thereof. Background Art

[0002] In industrial production, most metals and their alloys are susceptible to corrosion from solvents or moisture in the environment, which can lead to deterioration of metal material performance or even failure of material performance. Anti-corrosion coatings can isolate the underlying metal from the corrosive medium, thereby reducing the risk of corrosion. However, the corrosion resistance of commonly used coatings is insufficient, making it difficult to achieve long-term protection of metal materials. Using functional nanofillers to improve the anti-corrosion performance of coatings is currently a relatively effective composite method, but the raw materials currently used to improve nanofillers are mostly non-renewable materials, which are more harmful to the environment and lack long-term anti-corrosion capabilities. Unmodified nanofillers lack the corresponding anti-corrosion function due to structural limitations and cannot improve the anti-corrosion performance of the coating. Summary of the invention

[0003] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the purpose of the present invention is to provide a graphene oxide filler, which is modified by using esterified lignin and zinc-containing monomers to enhance the photothermal conversion ability of the graphene oxide filler, give it a self-repairing function, and improve its anti-corrosion performance.

[0004] A second aspect of the present invention provides a method for preparing a 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] A fifth aspect of the present invention provides an application of an anti-corrosion coating.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

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

[0010] The mass ratio of the graphene oxide to the esterified lignin is 1:(0.05-30); the mass ratio of the graphene oxide to the 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, and uses the zinc-containing monomers and esterified lignin to modify the graphene oxide to obtain a graphene oxide filler with excellent anticorrosion performance. The graphene oxide filler can be well dispersed in a resin system and has good compatibility.

[0012] Lignin is widely available, green, environmentally friendly, renewable and carbon neutral. Using it as a modifier for graphene oxide can not only solve the problems of poor dispersibility and compatibility of graphene oxide in coating resin systems, but also increase the added value of biomass materials. The modification of esterified lignin not only affects the anti-corrosion performance of graphene oxide filler, but also affects the dispersibility, compatibility and interface interaction of graphene oxide filler in resin systems, which is beneficial to improve the anti-corrosion effect of coatings containing the graphene oxide filler.

[0013] Zinc-containing monomers refer to zinc-containing compounds, which have the characteristics of wide sources, low prices and excellent anti-corrosion properties. Using them as self-healing agents can give graphene oxide fillers self-healing properties. The self-healing properties mainly refer to the ability of zinc ions to react with hydroxides produced by corrosion to form a zinc hydroxide protective film, which prevents corrosion from continuing. At the same time, zinc-containing monomers can also enhance the photothermal conversion ability of graphene oxide fillers. The self-healing properties and photothermal conversion properties further enhance the anti-corrosion properties of graphene oxide. Using them in coatings to form coatings can extend the service life of products. In addition, zinc-containing monomers also affect the dispersibility, compatibility and interfacial interactions of graphene oxide fillers in resin systems.

[0014] In the present invention, in order to ensure the modification effect of esterified lignin and zinc-containing monomers on graphene oxide, effectively improve the self-repairing performance and photothermal conversion performance of graphene oxide filler, and improve its anti-corrosion performance, the mass ratio of esterified lignin, zinc-containing monomer and graphene oxide in the preparation raw materials is controlled within an appropriate range. Too high or too low an amount of esterified lignin and zinc-containing monomer is not conducive to the improvement of anti-corrosion performance and self-repairing performance.

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

[0016] Further 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] Further 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, reacting to obtain esterified lignin; the acyl chloride monomer comprises at least one of acetyl chloride, benzoyl chloride, propionyl chloride, dodecanoyl chloride, furoyl chloride, myristic chloride, heptanoyl chloride, and stearyl chloride.

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

[0024] The reaction activity of the small molecule monomer of acyl chloride is relatively high, and it can undergo esterification reaction with the hydroxyl group on lignin at room temperature or low temperature to obtain the desired esterified lignin.

[0025] More preferably, the reaction time is 24 to 120 hours.

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

[0027] Further preferably, the mixing method of the lignin and the acyl chloride monomer includes ultrasound; the ultrasound time is 10 to 60 minutes.

[0028] Further 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 neutralizer in an organic solvent, stabilized at a temperature of -5 to 5°C, and then mixed with the 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] The second aspect of the present invention provides a method for preparing the graphene oxide filler according to the first aspect of the present invention, comprising the following steps:

[0036] The graphene oxide and the esterified lignin are mixed and dissolved, and after a first reaction, the solid and the liquid are separated to obtain a solid A, which is dried to obtain a graphene oxide filler precursor;

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

[0038] The graphene oxide filler precursor obtained after esterification lignin grafting is electronegative, and the zinc ions of the zinc-containing monomer can be loaded onto the 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 first reaction time is 2 to 48 hours.

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

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

[0045] Preferably, the second reaction is carried out at a pH of 8-12.

[0046] More preferably, the second reaction is carried out at a pH of 8-10.

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

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

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

[0050] Further 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 uniform dispersion method includes ultrasound.

[0052] It should be understood that, in the present invention, the role of ultrasonic treatment is to disperse and mix the system uniformly without affecting the structure and performance 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 time is 30 to 200 minutes.

[0056] More preferably, the second reaction time is 100 to 150 minutes.

[0057] Preferably, the solid-liquid separation method includes centrifugation; and a washing step is also included after the centrifugation.

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

[0059] Further preferably, the catalyst includes at least one of 4-dimethylaminopyridine, triethylamine, 2-methylimidazole, boron trifluoride, benzyldimethylamine, and 2-ethyl-4-methylimidazole.

[0060] Further preferably, the amount of the catalyst used is 1-10% of the mass of graphene oxide.

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

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

[0063] The 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 comprises epoxy vinyl ester resin, solvent and additives; the mass percentage of the graphene oxide filler in the anti-corrosion coating is 0.05-2%.

[0065] Further preferably, the mass percentage of the graphene oxide filler in the anti-corrosion coating is 0.05-1%.

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

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

[0068] Further preferably, the anti-corrosion coating comprises the following components by mass percentage: 60-80% epoxy vinyl ester resin, 0.1-0.5% graphene oxide filler, 1-2% additive, 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 comprises styrene.

[0071] Preferably, the auxiliary agent comprises cobalt naphthenate and / or 2-butanone peroxide.

[0072] The fourth aspect of the present invention provides a method for preparing the anticorrosive coating according to the third aspect of the present invention, comprising the following steps:

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

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

[0075] Preferably, the mixing means comprises ultrasound.

[0076] The fifth aspect of the present invention provides a use of the anti-corrosion paint described in the third aspect of the present invention in the preparation of an anti-corrosion coating.

[0077] Preferably, the anti-corrosion coating includes an anti-corrosion coating of equipment, instruments, ships, household items, decorations or engineering construction materials.

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

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

[0080] Compared with the prior art, the present invention has the following beneficial effects:

[0081] (1) The present invention adopts molecular structure design and composite reinforcement strategy to prepare graphene oxide filler with esterified lignin and zinc-containing monomer as modifiers. By adjusting the dosage range of esterified lignin and zinc-containing monomer, the anti-corrosion performance of graphene oxide filler is effectively improved, and it is endowed with photothermal conversion ability and self-repairing performance, which solves the problems of poor dispersibility and compatibility of graphene oxide filler in resin system. In addition, the raw material lignin used is a renewable and environmentally friendly raw material. While solving the problem that the modifier of anti-corrosion functional filler used in existing coatings has great harm to the environment, the application effect of graphene oxide filler is improved, and the anti-corrosion effect of coatings containing the graphene oxide filler is enhanced.

[0082] (2) The anti-corrosion coating of the present invention contains specific graphene oxide fillers. 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 capacity of the coating.

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

[0084] (4) The anti-corrosion coating of the present invention contains graphene oxide filler, and the coating formed by the graphene oxide filler has excellent anti-corrosion effect and also has photothermal conversion performance. The self-repairing property given by the zinc ions in the graphene oxide filler enables it to generate a layer of zinc hydroxide protective film covering the surface when the metal is corroded to generate hydroxide, thereby achieving a self-repairing anti-corrosion effect and significantly improving the anti-corrosion ability of the coating. The coating is suitable for preparing anti-corrosion coatings for equipment, instruments, ships, household items, decorations or engineering buildings, thereby extending the service life of metal products. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] Figure 1 The reaction scheme for preparing the anti-corrosion coating according to the embodiment of the present invention is shown in FIG.

[0086] Figure 2 This is the infrared spectrum of the esterified lignin used in Example 1 of the present invention.

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

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

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

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

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

[0092] Figure 8 The temperature curves of the coatings of Examples 2 to 4 of the present invention and Comparative Example 1 within 180 seconds. DETAILED DESCRIPTION

[0093] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

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

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

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

[0097] Example 1

[0098] This embodiment provides a graphene oxide filler, and the preparation method comprises 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 are added to a flask and dissolved in 50 mL of N,N-dimethylformamide; the mixture is stirred at 150°C for 5 hours and then centrifuged, the product is washed with N,N-dimethylformamide and anhydrous ethanol, and lignin-modified GO is obtained after drying; next, 0.1 g of lignin-modified GO is dispersed in 50 mL of deionized water and ultrasonically dispersed for 10 minutes; then, 0.15 g of Zn(NO3)2·6H2O is added, and the pH value is adjusted to 8 with NaOH (10 wt%) solution; the mixture is reacted at 60°C for 2 hours, centrifuged, washed and filtered; finally, the product is dried at 60°C for 24 hours to obtain graphene oxide filler, which is recorded as Zn@LGO.

[0100] The Zn@LGO of Example 1 is used to prepare the anticorrosive coatings of Examples 2 to 4. The reaction scheme during the preparation of the anticorrosive coatings is as follows: Figure 1 shown.

[0101] Example 2

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

[0103] The preparation method of the anticorrosive coating is as follows:

[0104] 3 g of a styrene solution of epoxy vinyl ester resin with a mass fraction of 70 wt% was added to a glass bottle, and then 0.1 wt% of Zn@LGO was added and ultrasonically dispersed; subsequently, 0.3 wt% of cobalt cyclopentaneate and 1.0 wt% of 2-butanone peroxide were added to the system, and the mixture was stirred evenly to obtain an anti-corrosion coating.

[0105] Example 3

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

[0107] The preparation method of the anticorrosive coating is as follows:

[0108] 3 g of a styrene solution of epoxy vinyl ester resin with a mass fraction of 70 wt% was added to a glass bottle, and then 0.2 wt% of Zn@LGO was added and ultrasonically dispersed; subsequently, 0.3 wt% of cobalt cyclopentaneate and 1.0 wt% of 2-butanone peroxide were added to the system, and the mixture was stirred evenly to obtain an anti-corrosion coating.

[0109] Example 4

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

[0111] The preparation method of the anticorrosive coating is as follows:

[0112] 3 g of a styrene solution of epoxy vinyl ester resin with a mass fraction of 70 wt% was added to a glass bottle, and then 0.4 wt% of Zn@LGO was added and ultrasonically dispersed; subsequently, 0.3 wt% of cobalt cyclopentaneate and 1.0 wt% of 2-butanone peroxide were added to the system, and the mixture was stirred evenly to obtain an anti-corrosion coating.

[0113] Comparative Example 1

[0114] This comparative example provides a coating, in which Zn@LGO is not added compared with Example 1, and the preparation method is as follows:

[0115] 3 g of 70 wt% epoxy vinyl ester resin solution was added into a glass bottle, and then 0.3 wt% of cobalt cyclopentaneate and 1.0 wt% of 2-butanone peroxide were added, and the mixture was mixed evenly to obtain an anti-corrosion coating.

[0116] Next, in order to verify the performance of the coating prepared by the anticorrosive coating of the present invention, the coatings prepared in Examples 2 to 4 and Comparative Example 1 were cured into coatings, and performance tests were performed on them.

[0117] 1. Preparation of coating

[0118] The coatings prepared in Examples 2 to 4 and Comparative Example 1 were coated on the surface of steel plates using an applicator, and placed in an oven at 25°C overnight. Each steel plate coated with the coating was then heated and cured at 100°C, 130°C, 160°C and 180°C in sequence, with the curing time being 3h, 2h, 2h and 2h, respectively, to obtain coatings. The coatings obtained in Comparative Example 1 and Examples 2 to 4 were respectively recorded as VER-0 (Comparative Example 1), VER-1 (Example 2), VER-2 (Example 3) and VER-3 (Example 4).

[0119] 2. Test methods

[0120] (1) Chemical structure characterization

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

[0122] (2)XPS test

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

[0124] (3) Electrochemical test

[0125] Test method: The electrochemical test data of the coating was obtained using an electrochemical workstation (CHI-660E). During the test, the corrosive medium was 3.5wt% salt water, the Ag / AgCl electrode was used as the reference electrode, and the platinum plate was used as the counter electrode.

[0126] (4) Photothermal conversion performance

[0127] Test method: Use near infrared light source (1.0W cm -2 , FU980AD1200-GD22) was used to evaluate the photothermal conversion performance of the samples and record the temperature changes of the samples during different irradiation times.

[0128] 3. Test results

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

[0130] Table 1 Performance test results of coating

[0131]

[0132] Combine the following Figures 2 to 8 The anti-corrosion coating, esterified lignin and graphene oxide filler of the present invention are analyzed as shown in Table 1.

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

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

[0135] contrast Figure 4 , Figure 5 , Figure 6 , Figure 7 From the results in Table 1, it can be found that the coatings formed by the coatings of the embodiment and the comparative example have similar impedance values ​​at the beginning of immersion. After the coatings are immersed in salt water for 100 days, the impedance modulus of the coatings is reduced, which indicates that the anti-corrosion performance of the coatings has weakened. Among them, the modulus of the coating of comparative example 1 is reduced to 5.0×10 7 Ω·cm 2 , indicating that its anti-corrosion performance is poor. In Examples 2 to 4, when Zn@LGO is added to the coating, the anti-corrosion performance of the coating is improved, and the impedance modulus decreases slightly. The impedance modulus of the coatings in Examples 2, 3, and 4 are 4.6×10 8 Ω·cm 2 , 1.1×10 9 Ω·cm 2 and 1.3×10 9 Ω·cm 2 Among them, the impedance modulus of the coating obtained in Example 4 is the largest, which is 2 orders of magnitude higher than that of the comparative example, which indicates that the anti-corrosion performance of the coating is enhanced with the increase of the Zn@LGO content. It should be noted that the higher the Zn@LGO content, the better, because the compatibility of the system and the dispersibility of Zn@LGO must also be considered.

[0136] Combination Figure 8 As can be seen from Table 1, within a few seconds of near-infrared irradiation of the coatings in the examples and comparative examples, their surface temperatures increased rapidly, and after the coatings were irradiated for 50 seconds, their surface temperatures changed little. After the coatings were irradiated for 180 seconds, the surface temperatures of the coatings in comparative example 1 and example 2, example 3, and example 4 were 81.9°C, 114.3°C, 122.1°C, and 139.2°C, respectively. This shows that adding Zn@LGO to the resin coating can give the coating excellent photothermal conversion properties and self-healing properties, thereby further improving the anti-corrosion effect of the coating and enhancing the protective effect of the coating.

[0137] In summary, the graphene oxide filler of the present invention has excellent anticorrosion performance, and has both light-heat conversion capability, and also has a self-repairing function when used in coatings, and has good dispersibility and compatibility in resin systems. The graphene oxide filler is suitable for preparing anticorrosion coatings. When the anticorrosion coating forms a coating, the "maze effect", dense three-dimensional network structure and self-repairing function formed by the graphene oxide filler have a synergistic anticorrosion effect, and the formed coating has excellent anticorrosion performance. Therefore, the anticorrosion coating of the present invention is suitable for preparing anticorrosion coatings, and is particularly suitable for preparing anticorrosion coatings for equipment, instruments, ships, household goods, decorations or engineering buildings, and prolonging the service life of metal products.

[0138] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A graphene oxide filler, characterized in that: The preparation raw materials include esterified lignin, zinc-containing monomers and graphene oxide; The mass ratio of the graphene oxide to the esterified lignin is 1:(0.05-30); the mass ratio of the graphene oxide to the zinc-containing monomer is 1:(0.05-50).

2. The graphene oxide filler according to claim 1, characterized in that The zinc-containing monomer includes at least one of zinc nitrate, zinc stearate, and zinc sulfate; And / or, the esterified lignin is prepared by a method comprising the following steps: mixing lignin with an acyl chloride monomer, reacting to obtain esterified lignin; the acyl chloride monomer comprises at least one of acetyl chloride, benzoyl chloride, propionyl chloride, dodecanoyl chloride, furoyl chloride, myristic chloride, heptanoyl chloride, and stearoyl chloride.

3. A method for preparing the graphene oxide filler according to claim 1 or 2, characterized in that: The following steps are involved: The graphene oxide and the esterified lignin are mixed and dissolved, and after a first reaction, the solid and the liquid are separated to obtain a solid A, which is dried to obtain a graphene oxide filler precursor; The graphene oxide filler precursor is mixed with the zinc-containing monomer, and after a second reaction, solid-liquid separation is performed to obtain a solid B, which is then dried to obtain the graphene oxide filler.

4. The preparation method according to claim 3, characterized in that: The temperature of the first reaction is 100-200°C; And / or, the second reaction is carried out at a pH of 8 to 12; And / or, the temperature of the second reaction is 50-80°C.

5. An anti-corrosion coating, characterized in that: The invention comprises the graphene oxide filler as described in any one of claims 1 to 2, or the graphene oxide filler prepared by the preparation method as described in any one of claims 3 to 4.

6. The anticorrosive coating according to claim 5, characterized in that: The anti-corrosion coating also includes epoxy vinyl ester resin, solvent and auxiliary agent; the mass percentage of the graphene oxide filler in the anti-corrosion coating is 0.05-2%.

7. The anticorrosive coating according to claim 6, characterized in that: The anticorrosive coating comprises the following components by mass percentage: 50-90% epoxy vinyl ester resin, 0.05-2% graphene oxide filler, 0.01-3% auxiliary agent, and the balance is solvent.

8. The anticorrosive coating according to claim 6, characterized in that: The solvent includes styrene; And / or, the auxiliary agent includes cobalt naphthenate and / or 2-butanone peroxide.

9. A method for preparing the anticorrosive coating according to any one of claims 5 to 8, characterized in that: The following steps are involved: The components are mixed to obtain the anti-corrosion coating.

10. Use of the anti-corrosion paint according to any one of claims 5 to 8 in the preparation of an anti-corrosion coating.

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