Ternary polymerization nano anticorrosive material and preparation method thereof

Abstract

The invention provides a ternary polymerization nanometer anti-corrosion material and a preparation method thereof, and belongs to the technical field of anti-corrosion materials. The coating is prepared from the following raw materials in parts by weight: 40-50 parts of an epoxy resin-acrylate-chitosan terpolymer, 8-12 parts of a nano modifier, 0.2-0.3 part of a flatting agent, 3-5 parts of a toughening agent, 0.1-0.3 part of a defoaming agent and 40-80 parts of water, the nano modifier is a nano material prepared by coating polyaniline on the surface of an intercalated MXene material, depositing graphene quantum dots and perovskite quantum dots, and coupling phytic acid and TiO2. The ternary polymerization nano anticorrosive material prepared by the invention has the advantages of better environmental protection performance, lower cost, better anticorrosive and antibacterial properties, good mechanical properties, good adhesive force, good gloss, fullness, weather resistance, good flame retardance and good compactness, and has wide application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-corrosion materials, and in particular to a ternary polymer nano anti-corrosion material and a preparation method thereof. Background Art

[0002] Since the beginning of the 21st century, the marine economy has received increasing attention from countries around the world. my country has clearly stated that its marine strategy is an important part of its economic development strategy. The development of the marine economy is inseparable from the support of marine engineering equipment. Currently, the main materials of marine engineering equipment are still mainly traditional metal materials. However, metal materials will suffer from serious corrosion problems in harsh marine environments such as high humidity, high salt and high temperature, which greatly reduces the service life of marine engineering equipment. Metal corrosion has brought huge economic losses, environmental pollution and safety hazards to the development of the marine economy. The corrosion process of marine engineering equipment mainly comes from chemical or electrochemical corrosion between the metal surface and the marine corrosive medium. Therefore, it is particularly important to develop advanced anti-corrosion materials and new and efficient special anti-corrosion technologies for metal surfaces that are adapted to the complex marine corrosive environment.

[0003] For metal materials, surface coatings are crucial for corrosion protection. Graphene is a single-layer, two-dimensional, flat film material composed of carbon atoms arranged in a hexagonal honeycomb lattice using sp2 hybridized orbitals. Graphene's unique structure imparts exceptional chemical stability and a large surface area, as well as excellent barrier, hydrophobic, antibacterial, thermal, and electrical conductivity. These exceptional properties give graphene a natural advantage in blocking marine corrosive media such as water, oxygen, and chloride ions. In recent years, graphene films have been widely used in the corrosion protection of metal surfaces in marine engineering equipment. While defect-free graphene films offer excellent corrosion protection for metals, studies have found that graphene films deposited using chemical vapor deposition (CVD) on Cu, Ni, and other alloys are prone to defects such as pores and microcracks within the graphene lattice. Corrosive media can easily diffuse through these defects to the metal substrate surface, causing minor corrosion at the interfaces between graphene grains or between the graphene film and the metal substrate. Therefore, more researchers are adding graphene and its derivatives as anti-corrosion functional fillers to polymers to prepare polymer-based graphene composite anti-corrosion coatings with certain anti-corrosion capabilities. This new anti-corrosion coating technology offers advantages such as ease of operation, low cost, good selectivity, wide applicability, and energy conservation, making it a highly efficient, economical, and environmentally friendly universal method. Summary of the Invention

[0004] The purpose of the present invention is to propose a ternary polymer nano anti-corrosion material and a preparation method thereof, which has good environmental protection performance, low cost, good anti-corrosion and antibacterial properties, good mechanical properties, good adhesion, good gloss, fullness, weather resistance, flame retardancy, good density, and broad application prospects.

[0005] The technical solution of the present invention is achieved as follows: The present invention provides a ternary polymer nano anti-corrosion material, which is prepared from the following raw materials in parts by weight: 40-50 parts of epoxy resin-acrylate-chitosan ternary copolymer, 8-12 parts of nano modifier, 0.2-0.3 parts of leveling agent, 0.1-0.3 parts of defoaming agent and 40-80 parts of water; the nano modifier is a nano material prepared by coating polyaniline on the surface of an intercalated MXene material, depositing graphene quantum dots and perovskite quantum dots, and then coupling phytic acid and TiO2.

[0006] As a further improvement of the present invention, the preparation method of the epoxy resin-acrylate-chitosan terpolymer is as follows: S1. Preparation of olefinated chitosan: dissolve chitosan in methanesulfonic acid, add acryloyl chloride in an ice-water bath, continue stirring to react, add acetone-ether mixed solution for precipitation, filter, wash, and dry to obtain olefinated chitosan; S2. Preparation of chitosan-acrylate copolymer: add olefinated chitosan to water, add butyl acrylate, methyl methacrylate, and 1-vinyl-3-ethylimidazole tetrafluoroborate, add initiator under inert gas protection, heat and stir to react, add ethanol for precipitation, filter, wash, and dry to obtain chitosan-acrylate copolymer; S3. Preparation of epoxy resin-acrylate-chitosan terpolymer: mix chitosan-acrylate copolymer and D-230 epoxy resin, add to ether, stir to react, remove the solvent under reduced pressure, wash, and dry to obtain epoxy resin-acrylate-chitosan terpolymer.

[0007] As a further improvement of the present invention, the mass ratio of chitosan to acryloyl chloride in step S1 is 10-12:1-2, the stirring reaction time is 6-8 hours, and the volume ratio of acetone to ether in the acetone-ether mixed solution is 3-5:2.

[0008] As a further improvement of the present invention, the mass ratio of the olefinated chitosan, butyl acrylate, methyl methacrylate, 1-vinyl-3-ethylimidazole tetrafluoroborate and initiator in step S2 is 15-20:4-6:2-4:2-3:0.01-0.02, the initiator is selected from at least one of sodium persulfate, potassium persulfate, and ammonium persulfate, and the heating and stirring reaction temperature is 60-70°C and the time is 4-6 hours.

[0009] As a further improvement of the present invention, in step S3, the mass ratio of the chitosan-acrylate copolymer to the D-230 epoxy resin is 12-15:5-7, and the stirring reaction time is 4-6 hours.

[0010] As a further improvement of the present invention, the preparation method of the nanomodifier is as follows: T1. Preparation of intercalated MXene material: LiF is added to an HCl solution and stirred to dissolve, Ti3AlC2 is added, etching is performed, centrifugation is performed, washing is performed, the product is added to water, ultrasonicated in an ice bath, hydroxyethylene diphosphonic acid is added, and intercalation is performed with stirring to produce the intercalated MXene material; T2. Polyaniline surface coating: Aniline is dissolved in hydrochloric acid, precooled, the intercalated MXene material is added, stirred to react, an initiator is added, the reaction is performed in an ice-water bath, centrifuged, washing, and drying to produce the polyaniline-coated intercalated MXene material; T3. Preparation of cesium oleate: Cesium carbonate and oleic acid are dissolved in 1-octadecene and hydrothermally reacted under inert gas to produce a cesium oleate solution; T4. Deposition of graphene quantum dots / perovskite quantum dots: Add lead iodine to 1-octadecene and allow a hydrothermal reaction under inert gas. Then, add oleic acid and oleylamine, continue the hydrothermal reaction, increase the temperature, add cesium oleate, react, centrifuge at low speed, collect the supernatant, centrifuge at high speed, collect the precipitate, add it to water, add citric acid and polyaniline-coated intercalated MXene material, undergo a third hydrothermal reaction, centrifuge, wash, and dry to produce graphene quantum dots / perovskite quantum dots deposited with polyaniline-coated intercalated MXene material. T5. Phytic acid / TiO2 coupling: Add phytic acid, nano-titanium dioxide, sodium dihydrogen phosphate, and graphene quantum dots / perovskite quantum dots deposited with polyaniline-coated intercalated MXene material to water, allow a hydrothermal reaction, centrifuge, wash, and dry to produce a nano-modifier.

[0011] As a further improvement of the present invention, the concentration of the HCl solution in step T1 is 8-10 mol / L, the mass ratio of LiF, Ti3AlC2, and ‌hydroxyethylene diphosphonic acid is 1:0.9-1.1:0.1-0.2, the etching temperature is 35-45°C, the time is 44-52h, and the stirring intercalation time is 1-3h; the concentration of the hydrochloric acid in step T2 is 1-3 mol / L, the mass ratio of the aniline, the intercalated MXene material, and the initiator is 4-8:15-20:1-2, the initiator is sodium persulfate, potassium persulfate, or ammonium persulfate, the pre-cooling temperature is -2 to 0°C, the stirring reaction time is 20-40min, and the temperature of the ice-water bath reaction is 30-50min.

[0012] As a further improvement of the present invention, the mass ratio of cesium carbonate and oleic acid in step T3 is 1:4-6, and the conditions of the hydrothermal reaction are reaction at 110-130°C for 0.5-1.5h and reaction at 140-160°C for 20-40min; the mass ratio of lead iodine, oleic acid, oleylamine, cesium oleate, citric acid and polyaniline coated intercalated MXene material in step T4 is 1:4-6:4-6:8-10:7-10:30-50, the temperature of the hydrothermal reaction is 110-130°C, the time is 0.5-1.5h, the time of continuing the hydrothermal reaction is 20-40min, the temperature is raised to 140-160°C, and the reaction temperature is 140-160°C. The reaction time is 20-40s, the speed of the low-speed centrifugation is 7000-9000r / min, the time is 5-15min, the speed of the high-speed centrifugation is 11000-12000r / min, the time is 5-15min, the temperature of the third hydrothermal reaction is 190-210°C, and the time is 20-24h; the mass ratio of phytic acid, nano-titanium dioxide, sodium dihydrogen phosphate and graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene material in step S5 is 4-6:3-5:0.5-1:15-20, the temperature of the hydrothermal reaction is 120-140°C, and the time is 20-24h.

[0013] As a further improvement of the present invention, the leveling agent is BYK-333, and the defoaming agent is BYK-024.

[0014] The present invention further protects a method for preparing the above-mentioned ternary polymer nano anti-corrosion material, comprising the following steps: adding an epoxy resin-acrylate-chitosan ternary copolymer, a leveling agent, and a defoaming agent into water, stirring and mixing at 300-500 r / min for 1-2 hours, adding a nano modifier, and homogenizing at 6000-8000 r / min for 10-20 minutes to obtain the ternary polymer nano anti-corrosion material.

[0015] The present invention has the following beneficial effects: the present invention prepares an epoxy resin-acrylate-chitosan ternary copolymer, wherein chitosan is reacted with acryloyl chloride to give it a double bond, and then copolymerized with an acrylate monomer to prepare a chitosan-acrylate copolymer, and then the amino groups on the chitosan can react with the epoxy groups of the epoxy resin to couple the epoxy resin, thereby preparing an epoxy resin-chitosan-acrylate copolymer, so that the epoxy resin is water-soluble, has the excellent properties of the epoxy resin, and has the gloss, fullness, good weather resistance and other characteristics of the acrylic resin, and also has the excellent antibacterial property of chitosan. The prepared ternary copolymer forms an interpenetrating network structure and has the characteristics of high adhesion, strong flexibility and density. The three work together to solve the problems of poor adhesion and insufficient water resistance of traditional single resins, meets environmental protection requirements, and has excellent anti-corrosion performance. The natural polymer chitosan contains a variety of negatively charged functional groups, such as amino and phenolic hydroxyl groups, which can provide electrons to the empty outer orbitals of metals and form complexes with the metal surface, thereby forming a stable and dense chemical adsorption protective film on the surface of the metal substrate. This isolates the metal substrate surface from corrosive media in the external environment, inhibits metal corrosion, and achieves the purpose of corrosion inhibition. In addition, ionic liquid monomers are added to the copolymerization of polyacrylates. The addition of ionic liquids can improve the ion transport capacity of the polymer, giving the polymer electrolyte a high ionic conductivity, maintaining good conductivity and electrochemical properties in low-temperature environments, enhancing the mechanical strength of the polymer, and significantly improving its flame retardancy.

[0016] Anticorrosion coatings prepared by adding polyaniline to paints not only provide anodic protection but also significantly enhance the coating's adhesion to the substrate and its water barrier properties. However, due to its unique structural characteristics, polyaniline has poor solubility and poor compatibility with coating resins, which can easily cause coating defects and limit its large-scale application in coatings.

[0017] The present invention prepares a nano-modifier, which uses layered MXene material as a matrix and intercalates a slow-release agent, hydroxyethylene diphosphonic acid, which not only increases the interlayer spacing of the layered MXene material and increases its specific surface area, but also can slowly release hydroxyethylene diphosphonic acid, complex metal ions, and inhibit further corrosion of the metal. The surface is coated with polyaniline, and then graphene quantum dots and perovskite quantum dots are deposited on the surface. When the coating is damaged, the graphene quantum dots and perovskite quantum dots can be released. The carriers of the perovskite quantum dots can move quickly in its lattice, and the mobility is very high. The value is high, which can achieve efficient charge transmission and transfer, has metal anti-corrosion effect, and has low cost; graphene quantum dots have highly stable dispersibility and film-forming properties in water, can be evenly dispersed in the anti-corrosion coating to form a dense protective film, effectively blocking the contact between corrosive media such as water and oxygen and the metal matrix, thereby playing a physical shielding role to prevent metal corrosion. At the same time, it can induce the formation of a dense oxide layer on the surface of the metal matrix, enhance the corrosion resistance of the composite coating, play a role similar to that of a passivation film, and improve the corrosion resistance of the metal. The two have a synergistic effect.

[0018] Then, phytic acid was used as a bridge to couple nano-TiO2 and graphene quantum dots / perovskite quantum dots to deposit polyaniline-coated intercalated MXene materials. Phytic acid can also complex metal ions to improve the corrosion resistance of metals. At the same time, the high conductivity and layered structure of MXene materials promote charge transfer, polyaniline provides electrochemical passivation, and TiO2 realizes photocatalytic degradation of corrosive media. Graphene and perovskite quantum dots form heterojunctions with TiO2, which significantly improves the separation and transfer efficiency of photogenerated carriers, and effectively inhibits the recombination of electron-hole pairs, thereby enhancing the photocatalytic activity. This enables titanium dioxide to utilize visible light for catalysis, improves the photocatalytic efficiency, and further enhances the anti-corrosion effect.

[0019] The ternary polymer nano anticorrosive material prepared by the present invention has good environmental performance, low cost, good anticorrosion and antibacterial properties, good mechanical properties, good adhesion, good gloss, fullness, weather resistance, flame retardancy, good density, and has broad application prospects. DETAILED DESCRIPTION

[0020] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0021] Preparation Example 1 Preparation of epoxy resin-acrylate-chitosan terpolymer The method is as follows: S1. Preparation of olefinated chitosan: Dissolve 10 g of chitosan in 200 mL of methanesulfonic acid, add 1 g of acryloyl chloride in an ice-water bath, and continue stirring for 6 hours. Add 200 mL of an acetone-ether mixture to precipitate for 1 hour, filter, wash, and dry to obtain olefinated chitosan; the volume ratio of acetone to ether in the acetone-ether mixture is 3:2. S2. Preparation of chitosan-acrylate copolymer: Add 15 g of olefinated chitosan to 500 mL of water, add 4 g of butyl acrylate, 2 g of methyl methacrylate, and 2 g of 1-vinyl-3-ethylimidazolium tetrafluoroborate, and under nitrogen, add 0.01 g of sodium persulfate. Heat to 60°C and stir for 4 hours. Add 500 mL of ethanol to precipitate for 1 hour, filter, wash, and dry to obtain chitosan-acrylate copolymer. S3. Preparation of epoxy resin-acrylate-chitosan ternary copolymer: 12 g chitosan-acrylate copolymer and 5 g D-230 epoxy resin were mixed and added into 500 mL ether, stirred and reacted for 4 h, filtered, washed and dried to obtain epoxy resin-acrylate-chitosan ternary copolymer.

[0022] Preparation Example 2 Preparation of epoxy resin-acrylate-chitosan terpolymer The method is as follows: S1. Preparation of olefinated chitosan: Dissolve 12 g of chitosan in 200 mL of methanesulfonic acid, add 2 g of acryloyl chloride in an ice-water bath, and continue stirring for 8 hours. Then, add 200 mL of an acetone-ether mixture to precipitate for 1 hour. Filter, wash, and dry to obtain olefinated chitosan; the volume ratio of acetone to ether in the acetone-ether mixture is 5:2. S2. Preparation of chitosan-acrylate copolymer: Add 20 g of olefinated chitosan to 500 mL of water, along with 6 g of butyl acrylate, 4 g of methyl methacrylate, and 3 g of 1-vinyl-3-ethylimidazolium tetrafluoroborate. Under nitrogen, add 0.02 g of ammonium persulfate, heat to 70°C, and stir for 6 hours. Then, add 500 mL of ethanol to precipitate for 1 hour. Filter, wash, and dry to obtain chitosan-acrylate copolymer. S3. Preparation of epoxy resin-acrylate-chitosan ternary copolymer: 15 g chitosan-acrylate copolymer and 7 g D-230 epoxy resin were mixed and added into 500 mL ether, stirred for 6 h, filtered, washed, and dried to obtain epoxy resin-acrylate-chitosan ternary copolymer.

[0023] Preparation Example 3 Preparation of epoxy resin-acrylate-chitosan terpolymer The method is as follows: S1. Preparation of olefinated chitosan: Dissolve 11 g of chitosan in 200 mL of methanesulfonic acid, add 1.5 g of acryloyl chloride in an ice-water bath, and continue stirring for 7 hours. Then, add 200 mL of an acetone-ether mixture to precipitate for 1 hour. Filter, wash, and dry to obtain olefinated chitosan; the volume ratio of acetone to ether in the acetone-ether mixture is 4:2. S2. Preparation of chitosan-acrylate copolymer: Add 17 g of olefinated chitosan to 500 mL of water, along with 5 g of butyl acrylate, 3 g of methyl methacrylate, and 2.5 g of 1-vinyl-3-ethylimidazolium tetrafluoroborate. Under nitrogen, add 0.015 g of potassium persulfate, heat to 65°C, stir for 5 hours, add 500 mL of ethanol to precipitate for 1 hour, filter, wash, and dry to obtain chitosan-acrylate copolymer. S3. Preparation of epoxy resin-acrylate-chitosan ternary copolymer: 13 g chitosan-acrylate copolymer and 6 g D-230 epoxy resin were mixed and added into 500 mL ether, stirred for 5 h, filtered, washed, and dried to obtain epoxy resin-acrylate-chitosan ternary copolymer.

[0024] Comparative Preparation Example 1 Compared with Preparation Example 3, the difference is that step S1 is not performed.

[0025] The details are as follows: S1. Preparation of chitosan-acrylate mixture: 17 g of chitosan was added to 500 mL of 2 wt% aqueous acetic acid solution, 5 g of butyl acrylate, 3 g of methyl methacrylate, and 2.5 g of 1-vinyl-3-ethylimidazolium tetrafluoroborate were added. Under nitrogen protection, 0.015 g of potassium persulfate was added, and the mixture was heated to 65°C and stirred for 5 h. 500 mL of ethanol was added for precipitation for 1 h, and the mixture was filtered, washed, and dried to obtain a chitosan-acrylate mixture. S2. Preparation of epoxy resin-acrylate-chitosan ternary mixture: 13 g of chitosan-acrylate mixture and 6 g of D-230 epoxy resin were mixed and added to 500 mL of ether. The mixture was stirred for 5 h, filtered, washed, and dried to obtain an epoxy resin-acrylate-chitosan ternary mixture.

[0026] Comparative Preparation Example 2 Compared with Preparation Example 3, the difference is that 1-vinyl-3-ethylimidazole tetrafluoroborate is not added in step S2.

[0027] The details are as follows: S2. Preparation of chitosan-acrylate copolymer: 17 g of olefinated chitosan was added to 500 mL of water, along with 7.5 g of butyl acrylate and 3 g of methyl methacrylate. Under nitrogen, 0.015 g of potassium persulfate was added. The mixture was heated to 65°C and stirred for 5 h. 500 mL of ethanol was added for precipitation for 1 h. The mixture was filtered, washed, and dried to obtain chitosan-acrylate copolymer.

[0028] Comparative Preparation Example 3 Compared with Preparation Example 3, the difference is that step S3 is not performed.

[0029] The details are as follows: S1. Preparation of olefinic chitosan: 11 g of chitosan was dissolved in 200 mL of methanesulfonic acid, 1.5 g of acryloyl chloride was added in an ice-water bath, and the reaction was continued with stirring for 7 h. 200 mL of an acetone-ether mixed solution was added and precipitated for 1 h. The mixture was filtered, washed, and dried to obtain olefinic chitosan; the volume ratio of acetone to ether in the acetone-ether mixed solution was 4:2; S2. Preparation of chitosan-acrylate copolymer: 17 g of olefinated chitosan was added to 500 mL of water, along with 5 g of butyl acrylate, 3 g of methyl methacrylate, and 2.5 g of 1-vinyl-3-ethylimidazolium tetrafluoroborate. Under nitrogen, 0.015 g of potassium persulfate was added. The mixture was heated to 65°C and stirred for 5 h. 500 mL of ethanol was added for precipitation for 1 h. The mixture was filtered, washed, and dried to obtain chitosan-acrylate copolymer.

[0030] Comparative Preparation Example 4 Compared with Preparation Example 3, the difference is that steps S1 and S2 are not performed, and in step S3, the chitosan-acrylate copolymer is replaced by chitosan of equal mass.

[0031] Specifically, 13 g of chitosan and 6 g of D-230 epoxy resin were mixed and added into 500 mL of ether, stirred and reacted for 5 h, filtered, washed, and dried to obtain an epoxy resin-chitosan polymer.

[0032] Preparation Example 4 Preparation of Nano-Modifier The method is as follows: T1. Preparation of intercalated MXene material: add 10g LiF to 400mL 8mol / L HCl solution, stir to dissolve, add 10g Ti3AlC2, etch at 35℃ for 44h, centrifuge, wash, add the product to 200mL water, ultrasonicate in an ice bath for 2h, add 0.1g hydroxyethylene diphosphonic acid, stir and intercalate for 1h, centrifuge, wash, and dry to obtain intercalated MXene material; T2. Polyaniline surface coating: dissolve 0.4g aniline in 200mL 1mol / L hydrochloric acid, precool to -2℃, add 1.5g intercalated MXene material, stir and react for 20min, add 0.1g sodium persulfate, react in an ice water bath for 30min, centrifuge, wash, and dry to obtain polyaniline-coated intercalated MXene material; T3. Preparation of cesium oleate: dissolve 1g cesium carbonate and 4g oleic acid in 100mL In 1-octadecene, under nitrogen protection, the reaction was carried out at 110°C for 0.5 h and at 140°C for 20 min to prepare a cesium oleate solution. T4. Deposition of graphene quantum dots / perovskite quantum dots: 1 g of lead iodide was added to 50 mL of 1-octadecene and hydrothermally reacted at 110°C for 0.5 h under nitrogen protection. Then, 4 g of oleic acid and 4 g of oleylamine were added and the hydrothermal reaction continued for 20 min. The temperature was raised to 140°C, 8 g of cesium oleate was added, and the reaction was continued. The supernatant was collected and the precipitate was collected and added to 300 mL of water. 7 g of citric acid and 30 g of polyaniline-coated intercalated MXene material were added. The reaction was hydrothermally reacted at 190°C for 20 h. The reaction was then centrifuged, washed, and dried to prepare graphene quantum dots / perovskite quantum dots and polyaniline-coated intercalated MXene materials. T5. Coupling of phytic acid / TiO2: 4 g of phytic acid, 3 g of nano-titanium dioxide, 0.5 g of sodium dihydrogen phosphate and 15 g of graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene materials were added to 250 mL of water, hydrothermally reacted at 120 ° C for 20 h, centrifuged, washed and dried to obtain a nano-modifier.

[0033] Preparation Example 5 Preparation of Nano-Modifier The method is as follows: T1. Preparation of intercalated MXene material: add 10g LiF to 400mL 10mol / L HCl solution, stir to dissolve, add 10g Ti3AlC2, etch at 45℃ for 52h, centrifuge, wash, add the product to 200mL water, ultrasonicate in an ice bath for 2h, add 0.2g hydroxyethylene diphosphonic acid, stir and intercalate for 3h, centrifuge, wash, and dry to obtain intercalated MXene material; T2. Polyaniline surface coating: dissolve 0.8g aniline in 200mL 3mol / L hydrochloric acid, precool to 0℃, add 2g intercalated MXene material, stir and react for 40min, add 0.2g sodium persulfate, react in an ice water bath for 50min, centrifuge, wash, and dry to obtain polyaniline-coated intercalated MXene material; T3. Preparation of cesium oleate: dissolve 1g cesium carbonate and 6g oleic acid in 100mL In 1-octadecene, under nitrogen protection, the reaction was carried out at 130°C for 1.5 hours and at 160°C for 40 minutes to prepare a cesium oleate solution. T4. Deposition of graphene quantum dots / perovskite quantum dots: 1 g of lead iodide was added to 50 mL of 1-octadecene and hydrothermally reacted at 130°C for 1.5 hours under nitrogen protection. 6 g of oleic acid and 6 g of oleylamine were then added and the hydrothermal reaction continued for 40 minutes. The temperature was raised to 160°C, 10 g of cesium oleate was added, the reaction was continued, and the supernatant was collected. The precipitate was centrifuged at 9000 rpm for 15 minutes, and the supernatant was collected. The precipitate was centrifuged at 12000 rpm for 15 minutes, and the precipitate was added to 300 mL of water. 10 g of citric acid and 50 g of polyaniline-coated intercalated MXene material were added. The reaction was hydrothermally reacted at 210°C for 24 hours. The reaction was then centrifuged, washed, and dried to prepare graphene quantum dots / perovskite quantum dots and polyaniline-coated intercalated MXene materials. T5. Coupling of phytic acid / TiO2: 6 g of phytic acid, 5 g of nano-titanium dioxide, 1 g of sodium dihydrogen phosphate and 20 g of graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene materials were added to 250 mL of water, hydrothermally reacted at 140 ° C for 24 h, centrifuged, washed and dried to obtain a nano-modifier.

[0034] Preparation Example 6 Preparation of Nano-Modifier The method is as follows: T1. Preparation of intercalated MXene material: add 10g LiF to 400mL 9mol / L HCl solution, stir to dissolve, add 10g Ti3AlC2, etch at 40℃ for 48h, centrifuge, wash, add the product to 200mL water, ultrasonicate in an ice bath for 2h, add 0.15g hydroxyethylene diphosphonic acid, stir and intercalate for 2h, centrifuge, wash, and dry to obtain intercalated MXene material; T2. Polyaniline surface coating: dissolve 0.6g aniline in 200mL 2mol / L hydrochloric acid, precool to 0℃, add 1.7g intercalated MXene material, stir and react for 30min, add 0.15g potassium persulfate, react in an ice water bath for 40min, centrifuge, wash, and dry to obtain polyaniline-coated intercalated MXene material; T3. Preparation of cesium oleate: dissolve 1g cesium carbonate and 5g oleic acid in 100mL In 1-octadecene, under nitrogen protection, the reaction was carried out at 120°C for 1 hour and at 150°C for 30 minutes to prepare a cesium oleate solution. T4. Deposition of graphene quantum dots / perovskite quantum dots: 1 g of lead iodine was added to 50 mL of 1-octadecene and hydrothermally reacted at 120°C for 1 hour under nitrogen protection. 5 g of oleic acid and 5 g of oleylamine were then added and the hydrothermal reaction continued for 30 minutes. The temperature was raised to 150°C, 9 g of cesium oleate was added, the reaction was continued, and the supernatant was collected. The supernatant was collected and the precipitate was collected and added to 300 mL of water. 8.5 g of citric acid and 40 g of polyaniline-coated intercalated MXene material were also added. The reaction was hydrothermally reacted at 200°C for 22 hours. The reaction was then centrifuged, washed, and dried to prepare graphene quantum dots / perovskite quantum dots and polyaniline-coated intercalated MXene materials. T5. Coupling of phytic acid / TiO2: 5 g of phytic acid, 4 g of nano-titanium dioxide, 0.7 g of sodium dihydrogen phosphate and 17 g of graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene materials were added to 250 mL of water, hydrothermally reacted at 130 ° C for 22 h, centrifuged, washed and dried to obtain a nano-modifier.

[0035] Comparative Preparation Example 5 Compared with Preparation Example 6, the difference is that hydroxyethylene diphosphonic acid is not added in step T1.

[0036] The details are as follows: Preparation of MXene material: 10g LiF was added to 400mL 9mol / L HCl solution, stirred to dissolve, 10g Ti3AlC2 was added, and the mixture was etched at 40℃ for 48h. The mixture was centrifuged, washed, and dried to obtain MXene material.

[0037] Comparative Preparation Example 6 Compared with Preparation Example 6, the difference is that step T2 is not performed.

[0038] The details are as follows: T1. Preparation of intercalated MXene material: add 10g LiF to 400mL 9mol / L HCl solution, stir to dissolve, add 10g Ti3AlC2, etch at 40℃ for 48h, centrifuge, wash, add the product to 200mL water, ultrasonicate in an ice bath for 2h, add 0.15g hydroxyethylene diphosphonic acid, stir and intercalate for 2h, centrifuge, wash, and dry to obtain intercalated MXene material; T2. Preparation of cesium oleate: dissolve 1g cesium carbonate and 5g oleic acid in 100mL 1-octadecene, react at 120℃ for 1h and at 150℃ for 30min under nitrogen protection to obtain cesium oleate solution; T3. Deposition of graphene quantum dots / perovskite quantum dots: add 1g lead acid iodine to 50mL In 1-octadecene, under nitrogen protection, the reaction was hydrothermally reacted at 120°C for 1 h. Then, 5 g of oleic acid and 5 g of oleylamine were added and the hydrothermal reaction was continued for 30 min. The temperature was raised to 150°C, 9 g of cesium oleate was added, the reaction was carried out, and the mixture was centrifuged at 8000 rpm for 10 min. The supernatant was collected and the mixture was centrifuged at 11500 rpm for 10 min. The precipitate was collected and added to 300 mL of water. 8.5 g of citric acid and 40 g of intercalated MXene material were added. The mixture was hydrothermally reacted at 200°C for 22 h. The mixture was centrifuged, washed, and dried to produce a graphene quantum dot / perovskite quantum dot deposited intercalated MXene material. T4. Phytic acid / TiO2 coupling: 5 g of phytic acid, 4 g of nano-titanium dioxide, 0.7 g of sodium dihydrogen phosphate, and 17 g of graphene quantum dot / perovskite quantum dot deposited intercalated MXene material were added to 250 mL of water and hydrothermally reacted at 130°C for 22 h. The mixture was centrifuged, washed, and dried to produce a nano-modifier.

[0039] Comparative Preparation Example 7 Compared with Preparation Example 6, the difference is that no perovskite quantum dots are deposited in step T4.

[0040] The details are as follows: T4. Deposition of graphene quantum dots: Add 8.5 g of citric acid and 40 g of polyaniline-coated intercalated MXene material to 300 mL of water, hydrothermally react at 200°C for 22 h, centrifuge, wash, and dry to obtain graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene material.

[0041] Comparative Preparation Example 8 Compared with Preparation Example 6, the difference is that graphene quantum dots are not deposited in step T4.

[0042] The details are as follows: T4. Deposition of perovskite quantum dots: Add 1g of lead iodine to 50mL of 1-octadecene, and hydrothermally react at 120°C for 1h under nitrogen protection. Then add 5g of oleic acid and 5g of oleylamine, and continue the hydrothermal reaction for 30min. Raise the temperature to 150°C, add 9g of cesium oleate, react, centrifuge at 8000r / min for 10min, collect the supernatant, and centrifuge at 11500r / min for 10min. Collect the precipitate to obtain perovskite quantum dot deposition polyaniline-coated intercalated MXene material.

[0043] Comparative Preparation Example 9 Compared with Preparation Example 6, the difference is that step T4 is not performed.

[0044] The details are as follows: T1. Preparation of intercalated MXene material: 10g LiF was added to 400mL 9mol / L HCl solution, stirred to dissolve, 10g Ti3AlC2 was added, and the mixture was etched at 40℃ for 48h, centrifuged, washed, and the product was added to 200mL water. After ultrasonication in an ice bath for 2h, 0.15g hydroxyethylene diphosphonic acid was added, and the mixture was stirred and intercalated for 2h. The mixture was centrifuged, washed, and dried to obtain the intercalated MXene material. T2. Polyaniline surface coating: 0.6g aniline was dissolved in 200mL 2mol / L hydrochloric acid, precooled to 0℃, 1.7g intercalated MXene material was added, stirred and reacted for 30min, 0.15g potassium persulfate was added, and the mixture was reacted in an ice-water bath for 40min. The mixture was centrifuged, washed, and dried to obtain the polyaniline-coated intercalated MXene material. T3. Phytic acid / TiO2 coupling: 5 g of phytic acid, 4 g of nano-titanium dioxide, 0.7 g of sodium dihydrogen phosphate, and 17 g of polyaniline-coated intercalated MXene material were added to 250 mL of water and hydrothermally reacted at 130°C for 22 h. The mixture was centrifuged, washed, and dried to obtain a nano-modifier.

[0045] Comparative Preparation Example 10 Compared with Preparation Example 6, the difference is that step T5 is not performed.

[0046] The details are as follows: T1. Preparation of intercalated MXene material: add 10g LiF to 400mL 9mol / L HCl solution, stir to dissolve, add 10g Ti3AlC2, etch at 40℃ for 48h, centrifuge, wash, add the product to 200mL water, ultrasonicate in an ice bath for 2h, add 0.15g hydroxyethylene diphosphonic acid, stir and intercalate for 2h, centrifuge, wash, and dry to obtain intercalated MXene material; T2. Polyaniline surface coating: dissolve 0.6g aniline in 200mL 2mol / L hydrochloric acid, precool to 0℃, add 1.7g intercalated MXene material, stir and react for 30min, add 0.15g potassium persulfate, react in an ice water bath for 40min, centrifuge, wash, and dry to obtain polyaniline-coated intercalated MXene material; T3. Preparation of cesium oleate: dissolve 1g cesium carbonate and 5g oleic acid in 100mL In 1-octadecene, under nitrogen protection, the reaction was carried out at 120°C for 1 hour and at 150°C for 30 minutes to prepare a cesium oleate solution. T4. Deposition of graphene quantum dots / perovskite quantum dots: 1 g of lead iodine was added to 50 mL of 1-octadecene and hydrothermally reacted at 120°C for 1 hour under nitrogen protection. Then, 5 g of oleic acid and 5 g of oleylamine were added and the hydrothermal reaction continued for 30 minutes. The temperature was raised to 150°C, and 9 g of cesium oleate was added. The reaction was centrifuged at 8000 rpm for 10 minutes, and the supernatant was collected. The precipitate was centrifuged at 11500 rpm for 10 minutes, and the precipitate was collected and added to 300 mL of water. 8.5 g of citric acid and 40 g of polyaniline-coated intercalated MXene material were added. The reaction was hydrothermally reacted at 200°C for 22 hours. The reaction was centrifuged, washed, and dried to prepare graphene quantum dots / perovskite quantum dots deposited with polyaniline-coated intercalated MXene material, which is the nanomodifier.

[0047] Example 1

[0048] This example provides a ternary polymer nano-anticorrosive material, which is prepared from the following raw materials in parts by weight: 40 parts of the epoxy resin-acrylate-chitosan ternary copolymer prepared in Preparation Example 1, 8 parts of the nano-modifier prepared in Preparation Example 4, 0.2 parts of the leveling agent BYK-333, 0.1 parts of the defoaming agent BYK-024, and 40 parts of water.

[0049] The preparation method comprises the following steps: Epoxy resin-acrylate-chitosan ternary copolymer, leveling agent BYK-333, and defoaming agent BYK-024 were added to water, stirred and mixed at 300 r / min for 1 hour, and nano-modifier was added and homogenized at 6000 r / min for 10 minutes to prepare ternary polymer nano-anticorrosion material.

[0050] Example 2

[0051] This example provides a ternary polymer nano-anticorrosive material, which is prepared from the following raw materials in parts by weight: 50 parts of the epoxy resin-acrylate-chitosan ternary copolymer prepared in Preparation Example 2, 12 parts of the nano-modifier prepared in Preparation Example 5, 0.3 parts of the leveling agent BYK-333, 0.3 parts of the defoaming agent BYK-024, and 80 parts of water.

[0052] The preparation method comprises the following steps: Epoxy resin-acrylate-chitosan ternary copolymer, leveling agent BYK-333, and defoaming agent BYK-024 were added to water, stirred and mixed at 500 r / min for 2 hours, and nano-modifier was added and homogenized at 8000 r / min for 20 minutes to prepare ternary polymer nano-anticorrosion material.

[0053] Example 3

[0054] This example provides a ternary polymer nano anti-corrosion material, which is prepared from the following raw materials in parts by weight: 45 parts of the epoxy resin-acrylate-chitosan ternary copolymer prepared in Preparation Example 3, 10 parts of the nano modifier prepared in Preparation Example 6, 0.25 parts of the leveling agent BYK-333, 0.2 parts of the defoaming agent BYK-024, and 60 parts of water.

[0055] The preparation method comprises the following steps: Epoxy resin-acrylate-chitosan ternary copolymer, leveling agent BYK-333, and defoaming agent BYK-024 were added to water, stirred and mixed at 400 r / min for 1.5 hours, and nano-modifier was added and homogenized at 7000 r / min for 15 minutes to prepare ternary polymer nano-anticorrosion material.

[0056] Comparative Example 1 Compared with Example 3, the difference is that the epoxy resin-acrylate-chitosan terpolymer is prepared by Comparative Preparation Example 1.

[0057] Comparative Example 2 Compared with Example 3, the difference is that the epoxy resin-acrylate-chitosan terpolymer is prepared by Comparative Preparation Example 2.

[0058] Comparative Example 3 Compared with Example 3, the difference is that the epoxy resin-acrylate-chitosan terpolymer is prepared by Comparative Preparation Example 3.

[0059] Comparative Example 4 Compared with Example 3, the difference is that the epoxy resin-acrylate-chitosan terpolymer is prepared by Comparative Preparation Example 4.

[0060] Comparative Example 5 Compared with Example 3, the difference is that the nano-modifier is prepared by Comparative Preparation Example 5.

[0061] Comparative Example 6 Compared with Example 3, the difference is that the nano-modifier is prepared by Comparative Preparation Example 6.

[0062] Comparative Example 7 Compared with Example 3, the difference is that the nano-modifier is prepared by Comparative Preparation Example 7.

[0063] Comparative Example 8 Compared with Example 3, the difference is that the nano-modifier is prepared by Comparative Preparation Example 8.

[0064] Comparative Example 9 Compared with Example 3, the difference is that the nano-modifier is prepared by Comparative Preparation Example 9.

[0065] Comparative Example 10 Compared with Example 3, the difference is that the nano-modifier is prepared by Comparative Preparation Example 10.

[0066] Test Example 1 The ternary polymeric nano-anticorrosive materials prepared in Examples 1-3 and Comparative Examples 1-10 were sprayed onto test panels in accordance with the requirements of GB / T 1727-2021. The following tests were performed, and the results are shown in Table 1.

[0067] Adhesion test: Adhesion is tested according to GB / T5210-2006 coating adhesion test method (pull-off method).

[0068] Pencil hardness test refers to GB / T6739-2006.

[0069] Flexibility test refers to GB / T1731-2020.

[0070] The impact resistance test refers to GB / T1732-2020. The mass of the hammer is (1000±1)g. The paint film is magnified 4 times to observe whether it is damaged. The maximum hammer drop height when there is no damage is the measurement result.

[0071] Table 1

[0072] It can be seen from the above table that the ternary polymeric nano anti-corrosion materials prepared in Examples 1-3 of the present invention have good adhesion, flexibility and hardness, and good impact resistance.

[0073] Test Example 3 The ternary polymeric nano-anticorrosive materials prepared in Examples 1-3 and Comparative Examples 1-10 were sprayed onto test panels in accordance with the requirements of GB / T 1727-2021. The following tests were performed, and the results are shown in Table 2.

[0074] The neutral salt spray resistance test is carried out in accordance with GB / T1771-2007 “Determination of neutral salt spray resistance of paints and varnishes” on a JD-120 (600L) salt spray tester. The mass concentration of the sodium chloride solution is 55g / L and the pH is 6.7.

[0075] The acid and alkali resistance test was carried out in accordance with GB1763-1979. The test pieces were placed in the acid and alkali test box in turn. Dilute hydrochloric acid was added to the left side and NaOH solution was added to the right side. The paint film was observed every 1 hour to see if there was any cracking or damage. The time from adding the solution to the damage of the paint film was recorded.

[0076] The organic solvent resistance test is carried out according to the manual wiping method specified in GB / T23989-2009 "Determination of Solvent Resistance of Coatings by Wiping Method". A finger wrapped in absorbent cotton is used to wipe back and forth 25 times to observe whether the coating is damaged and the substrate is exposed.

[0077] Table 2

[0078] It can be seen from the above table that the ternary polymer nano anti-corrosion materials prepared in Examples 1-3 of the present invention have good salt spray resistance, acid and alkali resistance, and solvent resistance.

[0079] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A ternary polymer nano anti-corrosion material, characterized in that: The invention is prepared from the following raw materials in parts by weight: 40-50 parts of epoxy resin-acrylate-chitosan terpolymer, 8-12 parts of nano-modifier, 0.2-0.3 parts of leveling agent, 0.1-0.3 parts of defoaming agent and 40-80 parts of water; the nano-modifier is a nano-material prepared by coating polyaniline on the surface of an intercalated MXene material, depositing graphene quantum dots and perovskite quantum dots, and then coupling phytic acid and TiO2.

2. The ternary polymer nano anti-corrosion material according to claim 1, characterized in that: The preparation method of the epoxy resin-acrylate-chitosan terpolymer is as follows: S1. Preparation of olefinated chitosan: chitosan is dissolved in methanesulfonic acid, acryloyl chloride is added to an ice-water bath, stirring and reacting continuously, an acetone-ether mixed solution is added for precipitation, filtering, washing, and drying to obtain olefinated chitosan; S2. Preparation of chitosan-acrylate copolymer: olefinated chitosan is added to water, butyl acrylate, methyl methacrylate, and 1-vinyl-3-ethylimidazole tetrafluoroborate are added, initiator is added under inert gas protection, heating and stirring to react, ethanol is added for precipitation, filtering, washing, and drying to obtain chitosan-acrylate copolymer; S3. Preparation of epoxy resin-acrylate-chitosan terpolymer: chitosan-acrylate copolymer and D-230 epoxy resin are mixed and added to ether, stirring and reacting, solvent is removed under reduced pressure, washing, and drying to obtain epoxy resin-acrylate-chitosan terpolymer.

3. The ternary polymer nano anti-corrosion material according to claim 2, characterized in that: In step S1, the mass ratio of chitosan to acryloyl chloride is 10-12:1-2, the stirring reaction time is 6-8 hours, and the volume ratio of acetone to ether in the acetone-ether mixed solution is 3-5:

2.

4. The ternary polymer nano anti-corrosion material according to claim 2, characterized in that: In step S2, the mass ratio of the olefinated chitosan, butyl acrylate, methyl methacrylate, 1-vinyl-3-ethylimidazolium tetrafluoroborate and initiator is 15-20:4-6:2-4:2-3:0.01-0.02, the initiator is selected from at least one of sodium persulfate, potassium persulfate and ammonium persulfate, and the heating and stirring reaction temperature is 60-70° C. and the time is 4-6 hours.

5. The ternary polymer nano anti-corrosion material according to claim 2, characterized in that: In step S3, the mass ratio of the chitosan-acrylate copolymer to the D-230 epoxy resin is 12-15:5-7, and the stirring reaction time is 4-6 hours.

6. The ternary polymer nano anti-corrosion material according to claim 1, characterized in that: The nanomodifier preparation method is as follows: T1. Preparation of intercalated MXene material: LiF is added to an HCl solution and stirred to dissolve. Ti3AlC2 is added, etched, centrifuged, and washed. The product is added to water and ultrasonicated in an ice bath. Hydroxyethylene diphosphonic acid is added and stirred to intercalate the product to obtain the intercalated MXene material. T2. Polyaniline surface coating: Aniline is dissolved in hydrochloric acid, precooled, the intercalated MXene material is added, stirred to react, an initiator is added, the reaction is carried out in an ice-water bath, centrifuged, washed, and dried to obtain the polyaniline-coated intercalated MXene material. T3. Preparation of cesium oleate: Cesium carbonate and oleic acid are dissolved in 1-octadecene and hydrothermally reacted under inert gas to obtain a cesium oleate solution. T4. Deposition of graphene quantum dots / perovskite quantum dots: Add lead iodine to 1-octadecene, perform a hydrothermal reaction under inert gas protection, then add oleic acid and oleylamine, continue the hydrothermal reaction, increase the temperature, add cesium oleate, react, centrifuge at low speed, collect the supernatant, centrifuge at high speed, collect the precipitate, add water, add citric acid and polyaniline-coated intercalated MXene material, perform a third hydrothermal reaction, centrifuge, wash, and dry to obtain graphene quantum dots / perovskite quantum dots deposited with polyaniline-coated intercalated MXene material; T5. Phytic acid / TiO2 coupling: Phytic acid, nano-titanium dioxide, sodium dihydrogen phosphate, and graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene materials were added to water and hydrothermally reacted. The mixture was centrifuged, washed, and dried to obtain a nano-modifier.

7. The ternary polymer nano anti-corrosion material according to claim 6, characterized in that: The concentration of the HCl solution in step T1 is 8-10 mol / L, the mass ratio of LiF, Ti3AlC2, and ‌hydroxyethylene diphosphonic acid is 1:0.9-1.1:0.1-0.2, the etching temperature is 35-45°C, the time is 44-52h, and the stirring intercalation time is 1-3h; the concentration of the hydrochloric acid in step T2 is 1-3 mol / L, the mass ratio of the aniline, intercalated MXene material, and initiator is 4-8:15-20:1-2, the initiator is sodium persulfate, potassium persulfate, or ammonium persulfate, the pre-cooling temperature is -2 to 0°C, the stirring reaction time is 20-40min, and the temperature of the ice-water bath reaction is 30-50min.

8. The ternary polymer nano anti-corrosion material according to claim 6, characterized in that: The mass ratio of cesium carbonate and oleic acid in step T3 is 1:4-6, and the conditions of the hydrothermal reaction are 0.5-1.5h at 110-130°C and 20-40min at 140-160°C; the mass ratio of lead iodine, oleic acid, oleylamine, cesium oleate, citric acid and polyaniline-coated intercalated MXene material in step T4 is 1:4-6:4-6:8-10:7-10:30-50, the temperature of the hydrothermal reaction is 110-130°C, the time is 0.5-1.5h, the time of continuing the hydrothermal reaction is 20-40min, the temperature is raised to 140-160°C, and the reaction time is The reaction time is 20-40s, the rotation speed of the low-speed centrifugation is 7000-9000r / min, the time is 5-15min, the rotation speed of the high-speed centrifugation is 11000-12000r / min, the time is 5-15min, the temperature of the third hydrothermal reaction is 190-210°C, and the time is 20-24h; the mass ratio of phytic acid, nano-titanium dioxide, sodium dihydrogen phosphate and graphene quantum dots / perovskite quantum dots deposited polyaniline-coated intercalated MXene material in step S5 is 4-6:3-5:0.5-1:15-20, the temperature of the hydrothermal reaction is 120-140°C, and the time is 20-24h.

9. The ternary polymer nano anti-corrosion material according to claim 1, characterized in that: The leveling agent is BYK-333, and the defoaming agent is BYK-024.

10. A method for preparing the ternary polymer nano anti-corrosion material according to any one of claims 1 to 9, characterized in that: The following steps are involved: Epoxy resin-acrylate-chitosan ternary copolymer, leveling agent and defoaming agent are added into water, stirred and mixed at 300-500 r / min for 1-2 hours, nano modifier is added, homogenized at 6000-8000 r / min for 10-20 minutes, and ternary polymer nano anticorrosive material is prepared.

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