A solvent-resistant, rust-proof and corrosion-resistant bioresin coating and preparation method thereof

Abstract

The invention relates to the field of coatings and discloses a solvent-resistant, rust-proof and corrosion-resistant bio-resin coating and a preparation method thereof. The bio-resin coating comprises: a modified bio-based epoxy resin, a modified graphene oxide, a modified nano-titanium dioxide, a curing agent, and a diluent; the modified bio-based epoxy resin is prepared by modifying epoxidized polysiloxane formed by self-polymerization of siloxane; the modified nano-titanium dioxide is prepared by modifying a fluorine-containing group; and the modified graphene oxide is prepared by grafting a flame retardant modifier onto the surface of the graphene oxide. The flame retardant modifier is prepared by reacting 3-amino-1,2,4-triazole with hexachlorocyclotriphosphazene to prepare a flame retardant intermediate, and then grafting the flame retardant intermediate and gamma-aminopropyltriethoxysilane with terephthalaldehyde as a bridging agent, and further reacting with DOPO to prepare the bio-resin coating. The bio-resin coating prepared by the invention has strong adhesion, high pencil hardness, good corrosion resistance, solvent resistance and flame retardant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to a solvent-resistant, rust-proof and corrosion-resistant bio-resin coating and a preparation method thereof. Background Art

[0002] Biomass-based polymers are currently attracting increasing attention due to their widespread availability and environmental friendliness. Epoxy resin, a key thermosetting polymer, is widely used in coatings, adhesives, electronic components, architectural decoration, and other fields due to its excellent mechanical properties, adhesion, thermal performance, chemical stability, electrical insulation, and low cure shrinkage.

[0003] Epoxy resin is one of the most widely used thermosetting resins, with an annual global production of approximately 2 million tons, of which bisphenol A epoxy resin accounts for more than 85%. It is mainly made from two raw materials, bisphenol A and epichlorohydrin. Epichlorohydrin can be made from bio-based glycerol and has been industrialized. However, more than 67% of bisphenol A is currently completely dependent on petrochemical resources. At the same time, bisphenol A poses a great threat to the health of living organisms. The development of environmentally friendly resins that can replace bisphenol A epoxy resin is of great significance. At the same time, epoxy resin has a low limiting oxygen index and can burn in air after ignition at a relatively fast rate.

[0004] Environmentally friendly bio-based epoxy resin is a thermosetting resin with significant advantages in resource renewability, environmental compatibility, and molecular structure characteristics. It has attracted widespread attention as an alternative to traditional petroleum-based epoxy resins. As a new type of bio-sourced resin, bio-based epoxy resin can be obtained mainly through the development of renewable resources, such as through the epoxidation of renewable precursors such as vegetable oils, vanillin, lignin, cardanol, and itaconic acid, which can greatly reduce the consumption of petroleum resources. Compared with petroleum-based epoxy resins, bio-based epoxy resins have equally excellent performance. However, they are also flammable, which greatly limits their application in fields such as transportation, construction, and electronics. In addition, during the curing process to form a three-dimensional cross-linked network, micropores are easily formed on the surface of the epoxy resin coating. The resulting pores will seriously affect the epoxy resin's ability to block media, thereby causing corrosion and limiting the widespread application of the coating. Summary of the Invention

[0005] In order to address the deficiencies mentioned in the above background technology, the purpose of the present invention is to provide a solvent-resistant, rust-proof and corrosion-resistant bio-resin coating and a preparation method thereof. The coating is based on a modified bio-based epoxy resin, modified graphene oxide and modified nano-titanium dioxide are added, and the prepared coating has strong adhesion, high pencil hardness, good corrosion resistance, solvent resistance and flame retardant effect.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 50-70 parts of modified bio-based epoxy resin, 2-5 parts of modified graphene oxide, 10-15 parts of modified nano-titanium dioxide, 20-30 parts of curing agent, and 10-20 parts of diluent;

[0008] The modified bio-based epoxy resin is made by using epoxidized polysiloxane modified by self-polymerization of γ-glycidyloxypropyltrimethoxysilane to form a bio-based epoxy resin; the modified nano-titanium dioxide is made by grafting fluorine-containing groups onto nano-titanium dioxide;

[0009] The modified graphene oxide is prepared by grafting a flame retardant modifier onto the surface of graphene oxide, wherein the flame retardant modifier is prepared by a substitution reaction between 3-amino-1,2,4-triazole and hexachlorocyclotriphosphazene to form a flame retardant intermediate, and then the flame retardant intermediate and γ-aminopropyltriethoxysilane are grafted using terephthalaldehyde as a bridging agent, and further an addition reaction is carried out with DOPO to form the modified graphene oxide.

[0010] Preferably, the curing agent is a mixture of one or more of triethylenetetramine, 4,4'-diaminodiphenylmethane, and m-xylenediamine; and the diluent is a mixture of one or more of toluene, xylene, acetone, and butanone.

[0011] Preferably, the preparation method of the modified bio-based epoxy resin comprises the following steps:

[0012] A. Dissolve vanillin and tyramine in anhydrous ethanol, and reflux at 55-70° C. for 4-5 hours. After the reaction is complete, filter and dry to obtain component 1.

[0013] B. Component 1 and tetrabutylammonium bromide were dissolved in epichlorohydrin, and the mixture was refluxed at 75-85° C. for 4-6 hours, then cooled to 45-60° C., and sodium hydroxide solution was added dropwise to continue the reaction for 2-4 hours. After the reaction was completed, the solid was removed by filtration, and then diluted with distilled water. The organic solution obtained after separation was subjected to rotary evaporation and reduced pressure distillation to remove the solvent, thereby preparing a bio-based epoxy resin;

[0014] C. Dissolve γ-glycidyloxypropyltrimethoxysilane in a mixed solution of ethanol and deionized water, and continue stirring for 15 to 30 minutes. Then, add hydrochloric acid and continue stirring and reacting for 20 to 24 hours. After the reaction is completed, rotary evaporate to obtain epoxidized polysiloxane. Add bio-based epoxy resin to the epoxidized polysiloxane, place at 55 to 70° C. and stir for 5 to 8 hours to prepare a modified bio-based epoxy resin.

[0015] Preferably, the method for preparing the modified graphene oxide comprises the following steps:

[0016] (1) Hexachlorocyclotriphosphazene is placed in a reactor, acetonitrile is added to dissolve the mixture, the temperature is raised to 45-60° C., 3-amino-1,2,4-triazole is dissolved in deionized water, and the mixture is added to the reactor, stirred and mixed evenly, and then solid sodium hydroxide is added. The mixture is condensed and refluxed for 5-6 hours. After the reaction is completed, the mixture is subjected to rotary evaporation, washing, and drying to obtain a flame retardant intermediate.

[0017] (2) taking the flame retardant intermediate and γ-aminopropyltriethoxysilane into a reactor, adding ethanol solvent and ultrasonically dispersing them uniformly, taking terephthalaldehyde and dissolving it in ethanol and then adding it into the reactor, placing it under reflux at 55-65°C for 4-7h, then taking DOPO and dissolving it in ethanol and then adding it into the reactor, heating it to 75-85°C, and continuing the reaction for 5-7h. After the reaction is completed, filtering, washing, and drying are carried out to prepare a flame retardant modifier;

[0018] (3) Graphene oxide is ultrasonically dispersed in anhydrous ethanol, and then a flame retardant modifier is added. The mixture is stirred and reacted at 100-125° C. in a nitrogen atmosphere for 8-12 hours. After the reaction is completed, the modified graphene oxide is prepared by filtering, washing, and drying.

[0019] Preferably, the molar ratio of hexachlorocyclotriphosphazene to 3-amino-1,2,4-triazole in step (1) is 1:6 to 6.5.

[0020] Preferably, in step (2), the molar ratio of the flame retardant intermediate, γ-aminopropyltriethoxysilane, terephthalaldehyde and DOPO is 1:6-6.3:6-6.3:12-12.5.

[0021] Preferably, in step (3), the mass ratio of graphene oxide to flame retardant modifier is 1:0.5-1.

[0022] Preferably, the preparation method of the modified nano-titanium dioxide comprises the following steps: taking 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, anhydrous ethanol and deionized water in a reactor, stirring and mixing for 0.5 to 1 hour, then adding nano-titanium dioxide, and continuing to stir for 1 to 1.5 hours to prepare modified nano-titanium dioxide.

[0023] The preparation method of the solvent-resistant, rust-proof and corrosion-resistant bio-resin coating as described above comprises the following steps: weighing parts by weight of the raw materials, uniformly mixing the modified bio-based epoxy resin and the diluent, and then adding the modified graphene oxide, modified nano-titanium dioxide and the curing agent and stirring them uniformly to prepare the solvent-resistant, rust-proof and corrosion-resistant bio-resin coating.

[0024] Beneficial effects of the present invention:

[0025] The present invention uses vanillin, tyramine and epichlorohydrin as raw materials to prepare a bio-based epoxy resin containing a Schiff base structure, which has good degradability. In addition, the present invention uses siloxane to undergo a self-polymerization reaction to form an epoxidized polysiloxane, which can form a highly cross-linked network structure through ring-opening polymerization of epoxy groups. Therefore, the epoxidized polysiloxane can be co-cured with a curing agent containing an amino group together with the bio-based epoxy resin to form two cross-linked networks, thereby enhancing the density of the coating, improving its anti-corrosion effect and interfacial adhesion. The introduced polysiloxane structure can also improve the hydrophobicity and wear resistance of the coating. The polysiloxane is combined with modified nano-titanium dioxide modified with perfluorodecyltrimethoxysilane to form a super-hydrophobic surface of the coating by utilizing the strong hydrophobicity of the fluorine-containing group and the siloxane, thereby reducing direct contact between the coating and the corrosive environment, achieving the purposes of anti-corrosion, corrosion prevention and self-cleaning, and further improving the durability of the coating.

[0026] The invention utilizes six P-Cl bonds in the hexachlorocyclotriphosphazene structure to undergo substitution reactions with -NH groups in the 3-amino-1,2,4-triazole structure to prepare a flame retardant intermediate. Then, the flame retardant intermediate, terephthalaldehyde and γ-aminopropyltriethoxysilane are used as raw materials. The six amino groups in the flame retardant intermediate structure undergo Schiff base reactions with the aldehyde group at one end of the terephthalaldehyde to generate N=CH groups. At the same time, the amino group in the γ-aminopropyltriethoxysilane structure undergoes Schiff base reaction with the aldehyde group at the other end of the terephthalaldehyde to generate N=CH groups. Then, the PH bond in the DOPO structure undergoes addition reaction with the N=CH group to prepare a flame retardant containing multiple phosphorus elements and nitrogen elements. The flame retardant modifier imparts excellent flame retardant effect to the coating, and utilizes the silicon hydroxyl group introduced into the structure of the flame retardant modifier to undergo condensation reaction with graphene oxide to prepare modified graphene oxide, thereby combining the flame retardant modifier with graphene oxide through a strong chemical bond, avoiding the problems of migration and seepage of the flame retardant modifier, and ensuring that the coating achieves a long-term flame retardant effect. In addition, the grafting reaction expands the interlayer spacing of the graphene oxide, thereby making the path for the corrosive medium to reach the epoxy resin matrix to become tortuous, and at the same time is conducive to improving the dispersion uniformity of the graphene oxide, increasing the contact area between the graphene oxide and the epoxy resin matrix, and improving the compatibility between the graphene oxide and the epoxy resin matrix, so that the comprehensive performance of the graphene oxide is fully exerted. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0028] Example 1 A method for preparing a modified bio-based epoxy resin comprises the following steps:

[0029] A. Dissolve 15.2 g of vanillin and 13.7 g of tyramine in 150 mL of anhydrous ethanol, and reflux at 60° C. for 4 h. After the reaction is complete, filter and dry to obtain component 1.

[0030] B. Take 27.1g of component 1 and 3.2g of tetrabutylammonium bromide and dissolve them in 80mL of epichlorohydrin. Place them under reflux at 80°C for 4h, then cool to 50°C, add 16g of 40% sodium hydroxide solution by mass and continue to react for 3h. After the reaction is completed, filter to remove the solid, then add 60mL of dichloromethane to dilute, and wash with distilled water. The organic solution obtained after separation is subjected to rotary evaporation and reduced pressure distillation to remove the solvent to prepare a bio-based epoxy resin;

[0031] C. Take 10 g of γ-glycidyloxypropyltrimethoxysilane and dissolve it in a mixed solution of 18 mL of ethanol and 2 mL of deionized water, continue stirring for 30 minutes, then add 0.5 mL of hydrochloric acid and continue stirring and reacting for 24 hours. After the reaction is completed, rotary evaporation is performed to obtain epoxidized polysiloxane. Bio-based epoxy resin is added to the epoxidized polysiloxane, and the mixture is stirred and mixed at 60°C for 7 hours to prepare a modified bio-based epoxy resin.

[0032] Example 2 A method for preparing modified graphene oxide comprises the following steps:

[0033] (1) 0.87 g of hexachlorocyclotriphosphazene was placed in a reactor, 50 mL of acetonitrile solvent was added to dissolve the mixture, the temperature was raised to 55° C., 1.26 g of 3-amino-1,2,4-triazole was added to 50 mL of deionized water to dissolve the mixture, and the mixture was added to the reactor, stirred and mixed evenly, and then 0.6 g of sodium hydroxide solid was added. The mixture was condensed and refluxed for 5 h. After the reaction was completed, the mixture was subjected to rotary evaporation, washing, and drying to obtain a flame retardant intermediate.

[0034] (2) 6.3 g of flame retardant intermediate and 13.3 g of γ-aminopropyltriethoxysilane were placed in a reactor, 50 mL of ethanol solvent was added and ultrasonically dispersed uniformly, 8.3 g of terephthalaldehyde was added into 50 mL of ethanol to dissolve and then added into the reactor, and the mixture was refluxed at 65 ° C for 7 h, and then 26.1 g of DOPO was added into 100 mL of ethanol to dissolve and then added into the reactor, and the mixture was heated to 85 ° C and continued to react for 6 h. After the reaction was completed, the mixture was filtered, washed and dried to prepare a flame retardant modifier;

[0035] (3) 5 g of graphene oxide was ultrasonically dispersed in 120 mL of anhydrous ethanol, and then 3.1 g of a flame retardant modifier was added. The mixture was stirred and reacted at 125 ° C in a nitrogen atmosphere for 10 h. After the reaction was completed, the modified graphene oxide was prepared by filtering, washing, and drying.

[0036] Example 3 A method for preparing modified nano-titanium dioxide comprises the following steps:

[0037] 2 mL of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, 50 mL of anhydrous ethanol and 5 mL of deionized water were placed in a reactor and stirred for 1 hour. Then, 3.5 g of nano-titanium dioxide was added and stirred for 1 hour to prepare modified nano-titanium dioxide.

[0038] Example 4 A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 54 parts of the modified bio-based epoxy resin prepared in Example 1, 2 parts of the modified graphene oxide prepared in Example 2, 10 parts of the modified nano-titanium dioxide prepared in Example 3, 21 parts of the curing agent 4,4'-diaminodiphenylmethane, and 12 parts of the diluent acetone.

[0039] The preparation method of the above-mentioned solvent-resistant, anti-rust and anti-corrosion bio-resin coating includes the following steps: weighing each weight portion of raw materials, mixing the modified bio-based epoxy resin and the diluent evenly, and then adding modified graphene oxide, modified nano-titanium dioxide and a curing agent and stirring evenly to prepare the solvent-resistant, anti-rust and anti-corrosion bio-resin coating.

[0040] Example 5 A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 61 parts of the modified bio-based epoxy resin prepared in Example 1, 3 parts of the modified graphene oxide prepared in Example 2, 12 parts of the modified nano-titanium dioxide prepared in Example 3, 25 parts of the curing agent 4,4'-diaminodiphenylmethane, and 14 parts of the diluent acetone.

[0041] The preparation method of the above-mentioned solvent-resistant, rust-proof and corrosion-resistant bio-resin coating is the same as that of Example 4.

[0042] Example 6 A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 68 parts of the modified bio-based epoxy resin prepared in Example 1, 5 parts of the modified graphene oxide prepared in Example 2, 14 parts of the modified nano-titanium dioxide prepared in Example 3, 28 parts of the curing agent 4,4'-diaminodiphenylmethane, and 20 parts of the diluent acetone.

[0043] The preparation method of the above-mentioned solvent-resistant, rust-proof and corrosion-resistant bio-resin coating is the same as that of Example 4.

[0044] Comparative Example 1 A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 68 parts of the bio-based epoxy resin prepared in Example 1, 5 parts of the modified graphene oxide prepared in Example 2, 14 parts of the modified nano-titanium dioxide prepared in Example 3, 28 parts of a curing agent, 4,4'-diaminodiphenylmethane, and 20 parts of a diluent, acetone.

[0045] The preparation method of the above-mentioned solvent-resistant, rust-proof and corrosion-resistant bio-resin coating is the same as that of Example 4.

[0046] Comparative Example 2 A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 68 parts of the modified bio-based epoxy resin prepared in Example 1, 5 parts of graphene oxide, 14 parts of the modified nano-titanium dioxide prepared in Example 3, 28 parts of a curing agent, 4,4'-diaminodiphenylmethane, and 20 parts of a diluent, acetone.

[0047] The preparation method of the above-mentioned solvent-resistant, rust-proof and corrosion-resistant bio-resin coating is the same as that of Example 4.

[0048] Comparative Example 3 A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating comprises the following raw materials in parts by weight: 68 parts of the modified bio-based epoxy resin prepared in Example 1, 5 parts of the modified graphene oxide prepared in Example 2, 14 parts of nano-titanium dioxide, 28 parts of a curing agent, 4,4'-diaminodiphenylmethane, and 20 parts of a diluent, acetone.

[0049] The preparation method of the above-mentioned solvent-resistant, rust-proof and corrosion-resistant bio-resin coating is the same as that of Example 4.

[0050] Performance testing

[0051] The bio-resin coatings prepared in Examples 4-6 and Comparative Examples 1-3 were evenly coated on the surface of tinplate, dried and cured in an oven at 120°C, and after forming a coating film, experimental samples meeting the test specifications were prepared and subjected to the following performance tests: adhesion was measured using the cross-hatch method according to GB / T 9286-2021; water contact angle was measured using a PZ-200SD contact angle meter; pencil hardness was measured according to GB / T 6739-2022; media resistance was tested according to GB / T 9274-1988, with acid resistance being tested using a 10% sulfuric acid solution, alkali resistance being tested using a 10% sodium hydroxide solution, and salt water resistance being tested using a 5% sodium chloride solution, with the end time being when the paint film showed blistering, rusting, or severe discoloration; slight discoloration was allowed; and solvent resistance of the coating was evaluated by wiping the coating back and forth with a solvent-soaked absorbent cotton ball according to GB / T 23989-2009, with wrinkling and cracking of the film as signs of corrosion. The data results are shown in Table 1.

[0052] Table 1 Test results of sample performance

[0053]

[0054]

[0055] As can be seen from the data in Table 1, the coatings prepared in Examples 4-6 of the present invention have strong adhesion, high pencil hardness, good corrosion resistance, solvent resistance and flame retardant effect, and the water contact angle is greater than 150 °, with a super hydrophobic surface. Wherein the bio-based epoxy resin is not modified in Comparative Example 1, and the adhesion, water contact angle, pencil hardness and corrosion resistance measured are lower than those in Examples 4-6. The reason is that no epoxidized polysiloxane component is added. In Comparative Example 2, graphene oxide is not modified, and the water contact angle, pencil hardness and corrosion resistance measured are slightly worse than those in Examples 4-6. The flame retardant performance is significantly reduced compared to Examples 4-6. The reason is that no flame retardant modifier is grafted on the surface of graphene oxide. In Comparative Example 3, nano-titanium dioxide is not modified, and the water contact angle, pencil hardness and corrosion resistance measured are lower than those in Examples 4-6. This shows that the introduction of fluorine-containing groups can improve the corrosion resistance of the coating to a certain extent, and the pencil hardness is reduced due to the agglomeration of nano-titanium dioxide.

[0056] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0057] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A solvent-resistant, rust-proof and corrosion-resistant bio-resin coating, characterized in that: The invention comprises the following raw materials in parts by weight: 50-70 parts of modified bio-based epoxy resin, 2-5 parts of modified graphene oxide, 10-15 parts of modified nano-titanium dioxide, 20-30 parts of curing agent, and 10-20 parts of diluent; The modified nano titanium dioxide is prepared by grafting fluorine-containing groups onto nano titanium dioxide; The preparation method of the modified bio-based epoxy resin comprises the following steps: A. Dissolve vanillin and tyramine in anhydrous ethanol, and reflux at 55-70°C for 4-5 hours. After the reaction is complete, filter and dry to obtain component 1. B. Component 1 and tetrabutylammonium bromide were dissolved in epichlorohydrin, and the mixture was refluxed at 75-85°C for 4-6 hours, then cooled to 45-60°C, and sodium hydroxide solution was added dropwise to continue the reaction for 2-4 hours. After the reaction was completed, the solid was removed by filtration, and then diluted with distilled water. The organic solution obtained after separation was subjected to rotary evaporation and reduced pressure distillation to remove the solvent, thereby preparing a bio-based epoxy resin; C. Dissolve γ-glycidyloxypropyltrimethoxysilane in a mixed solution of ethanol and deionized water, continue stirring for 15-30 minutes, then add hydrochloric acid and continue stirring and reacting for 20-24 hours. After the reaction is completed, rotary evaporate to obtain epoxidized polysiloxane, add bio-based epoxy resin to the epoxidized polysiloxane, and stir and mix at 55-70° C. for 5-8 hours to prepare a modified bio-based epoxy resin; The preparation method of the modified graphene oxide comprises the following steps: (1) Hexachlorocyclotriphosphazene was placed in a reactor, acetonitrile was added to dissolve the mixture, the temperature was raised to 45-60°C, 3-amino-1,2,4-triazole was dissolved in deionized water and then added to the reactor, the mixture was stirred and mixed evenly, and then sodium hydroxide solid was added. The mixture was condensed and refluxed for 5-6 hours. After the reaction was completed, the mixture was subjected to rotary evaporation, washing, and drying to obtain a flame retardant intermediate. (2) Put the flame retardant intermediate and γ-aminopropyltriethoxysilane into the reactor, add ethanol solvent and ultrasonically disperse them evenly, take terephthalaldehyde and dissolve it in ethanol and then add it to the reactor, place it under reflux at 55-65°C for 4-7h, then take DOPO and dissolve it in ethanol and add it to the reactor, heat it to 75-85°C, continue to react for 5-7h, and after the reaction is completed, filter, wash and dry it to prepare the flame retardant modifier; (3) Graphene oxide is ultrasonically dispersed in anhydrous ethanol, and then a flame retardant modifier is added. The mixture is stirred and reacted at 100-125°C in a nitrogen atmosphere for 8-12 hours. After the reaction is completed, the modified graphene oxide is prepared by filtering, washing, and drying.

2. The solvent-resistant, rust-proof and corrosion-resistant bio-resin coating according to claim 1, characterized in that: The curing agent is a mixture of one or more of triethylenetetramine, 4,4'-diaminodiphenylmethane, and m-xylenediamine; and the diluent is a mixture of one or more of toluene, xylene, acetone, and butanone.

3. The solvent-resistant, rust-proof and corrosion-resistant bio-resin coating according to claim 1, characterized in that: In the step (1), the molar ratio of hexachlorocyclotriphosphazene to 3-amino-1,2,4-triazole is 1:6-6.

5.

4. The solvent-resistant, rust-proof and corrosion-resistant bio-resin coating according to claim 1, characterized in that: In the step (2), the molar ratio of the flame retardant intermediate, γ-aminopropyltriethoxysilane, terephthalaldehyde and DOPO is 1:6~6.3:6~6.3:12~12.

5.

5. The solvent-resistant, rust-proof and corrosion-resistant bio-resin coating according to claim 1, characterized in that: In the step (3), the mass ratio of graphene oxide to the flame retardant modifier is 1:0.5-1.

6. The solvent-resistant, rust-proof and corrosion-resistant bio-resin coating according to claim 1, characterized in that: The preparation method of modified nano-titanium dioxide comprises the following steps: adding 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, anhydrous ethanol and deionized water into a reactor, stirring and mixing for 0.5 to 1 hour, then adding nano-titanium dioxide, and continuing to stir for 1 to 1.5 hours to prepare modified nano-titanium dioxide.

7. The method for preparing the solvent-resistant, rust-proof and corrosion-resistant bio-resin coating according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: weighing parts by weight of raw materials, uniformly mixing modified bio-based epoxy resin and diluent, then adding modified graphene oxide, modified nano-titanium dioxide and curing agent and stirring evenly to prepare solvent-resistant, anti-rust and anti-corrosion bio-resin coating.

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