Hexagonal boron nitride stripping method, anti-corrosion paint and anti-corrosion coating

Abstract

The present invention provides a hexagonal boron nitride exfoliation method, an anti-corrosion paint, and an anti-corrosion coating. The hexagonal boron nitride exfoliation method comprises ball milling a mixture containing hexagonal boron nitride and an intercalation agent, wherein the intercalation agent comprises gallic blue. The present invention utilizes gallic blue-assisted ball milling to exfoliate the boron nitride, resulting in a boron nitride sheet material with excellent dispersion, addressing the problem of boron nitride easily stacking and difficult dispersion in resin. Furthermore, gallic blue can act as a corrosion inhibitor, further enhancing the anti-corrosion effectiveness of the coating.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal surface protection, and in particular relates to a method for stripping hexagonal boron nitride nanosheets, a method for preparing a gallic blue-boron nitride hybrid material, an anti-corrosion coating agent and an anti-corrosion coating. Background Art

[0002] Metal corrosion is a thorny problem that poses a threat to human safety and causes huge economic losses in various industries. Epoxy coatings stand out due to their excellent adhesion, chemical stability, and processability. However, cracks and pores are inevitable in the epoxy matrix, which leads to poor long-term corrosion protection of the coating. Corrosive media (such as O2, Cl-, H2O, etc.) will penetrate into the matrix through defects and then react with the metal. To address this problem, it has been demonstrated that the addition of two-dimensional (2D) materials as nanofillers to the matrix can promote the maze effect and improve the physical barrier properties of the coating, which is an effective means to solve the above problems.

[0003] Hexagonal boron nitride (h-BN) has a sp 2 Hybrid layered structures, with B and N arranged uniformly in a honeycomb configuration, continue to attract attention due to their exceptional thermal stability, wear resistance under certain conditions, and excellent barrier properties. Notably, h-BN combines the advantages of graphene with insulating properties, making it a promising candidate for long-term corrosion protection. However, weak van der Waals forces often lead to aggregation between adjacent layers, significantly limiting its ability to deliver excellent barrier properties in anti-corrosion coatings. To better disperse h-BN nanosheets in aqueous solutions, common exfoliation strategies include chemical modification and non-covalent modification. Compared to the former, non-covalent modification offers a simple and efficient way to achieve uniform dispersion while maximally preserving the original properties of h-BN. However, the layered materials exfoliated by existing methods primarily play a key role in providing a barrier effect during the initial stages of the corrosion process; they lack sufficient protection during the reaction phase. Consequently, existing coatings often incorporate corrosion inhibitors, which can introduce additional defects and pores into the epoxy matrix. Summary of the Invention

[0004] In order to solve all or part of the above technical problems, the present invention provides the following technical solutions:

[0005] One of the objectives of the present invention is to provide a method for exfoliating hexagonal boron nitride, comprising: ball milling a mixture containing hexagonal boron nitride and an intercalation agent, wherein the intercalation agent comprises gallic blue.

[0006] The structural formula of the gallic blue is as follows:

[0007]

[0008] The present invention uses gallic blue as an intercalant and cooperates with a ball milling method to obtain a hexagonal boron nitride (h-BN) sheet material with good dispersion effect, solving the problems of poor h-BN dispersibility, easy stacking and difficult dispersion in the coating. The coating formed by dispersing the h-BN obtained by peeling in the resin has a good barrier effect.

[0009] In some embodiments, the method specifically includes: uniformly mixing the hexagonal boron nitride, the intercalation agent, and the solvent to form a uniform mixture, and then performing the ball milling process on the mixture.

[0010] In some embodiments, the mass ratio of hexagonal boron nitride to gallic blue is 1:1 to 1.5.

[0011] In some embodiments, the ball milling process is performed at a rotation speed of 500 to 800 rpm, for a time of 8 to 10 hours, and with a grinding ball diameter of 1.6 mm to 1.8 mm.

[0012] In some embodiments, the grinding balls used in the ball milling process include zirconia ceramic balls, silica grinding balls, silicon carbide grinding balls, etc., but are not limited thereto.

[0013] In some embodiments, the thickness of the exfoliated hexagonal boron nitride nanosheets obtained by the method is 5 to 10 nm.

[0014] In some embodiments, the hexagonal boron nitride nanosheets obtained by the method after exfoliation are in the shape of discs, with a size of 1 to 2 μm and a thickness of 5 to 10 nm.

[0015] The stripping method adopted in the present invention can reduce the thickness of the hexagonal boron nitride layer by about 10 times, and the time required for stripping is relatively short (5 to 8 hours). Compared with other intercalating agents based on non-π interaction, gallic blue exhibits higher stripping efficiency and good stripping effect.

[0016] A second object of the present invention is to provide a method for preparing a gallic blue-boron nitride hybrid material, comprising ball-milling a mixture containing hexagonal boron nitride and gallic blue to obtain the gallic blue-boron nitride hybrid material. In this preparation method, gallic blue acts as an intercalating agent to improve the dispersion of h-BN. Furthermore, the gallic blue molecules in the hybrid material can be adsorbed on the surface of the substrate, acting as a corrosion inhibitor to provide active protection, further enhancing the anti-corrosion performance of the coating.

[0017] In some embodiments, the mass ratio of hexagonal boron nitride to gallic blue is 1:1 to 1.5.

[0018] In some embodiments, the ball milling process is performed at a rotation speed of 500 to 800 rpm, for a time of 8 to 10 hours, and with a grinding ball diameter of 1.6 mm to 1.8 mm.

[0019] In some embodiments, the grinding balls used in the ball milling process include zirconia ceramic balls, silica grinding balls, silicon carbide grinding balls, etc., but are not limited thereto.

[0020] In some embodiments, the hexagonal boron nitride, gallic blue, and solvent are uniformly mixed to form a homogeneous mixture, and then the mixture is subjected to the ball milling process.

[0021] In some embodiments, after the ball milling process is completed, the ball milling product is subjected to solid-liquid separation, and the solid product obtained by solid-liquid separation is freeze-dried to obtain a gallic blue-boron nitride hybrid material that can be directly dispersed in a resin. The solid-liquid separation is performed, for example, by centrifugation at a speed of 8,000 to 10,000 rpm, but is not limited thereto.

[0022] A third object of the present invention is to provide a gallic blue-boron nitride hybrid material obtained according to any one of the preparation methods described.

[0023] A fourth object of the present invention is to provide an anti-corrosion coating comprising: 2500-3000 parts by mass of a polyetheramine-modified epoxy resin, 15-20 parts by mass of the gallic blue-boron nitride hybrid material, 600-1000 parts by mass of a first polyetheramine, and 100 parts by mass of a solvent. The first polyetheramine and the solvent function to adjust the viscosity, making the anti-corrosion coating convenient for engineering applications and more environmentally friendly.

[0024] In some embodiments, the first polyetheramine includes one or a combination of polyetheramine D230 and polyetheramine D400, but is not limited thereto.

[0025] In some embodiments, the solvent includes one or more of benzene, toluene, xylene, or propylene glycol monomethyl ether acetate, but is not limited thereto.

[0026] In some embodiments, the raw materials for the polyetheramine-modified epoxy resin include 3,000 to 4,000 parts by mass of a base epoxy resin and 1,000 to 1,500 parts by mass of a second polyetheramine. Modifying the epoxy resin with the second polyetheramine before formulating the coating significantly reduces the viscosity of the oil-based epoxy resin compared to directly formulating the coating with the epoxy resin, facilitating its application in engineering projects and better meeting environmental requirements.

[0027] In some embodiments, the matrix epoxy resin includes epoxy resin E51, epoxy resin E20, epoxy resin E44, etc., but is not limited thereto.

[0028] In some embodiments, the second polyetheramine includes polyetheramine M1000, polyetheramine M2070, or polyetheramine M600, but is not limited thereto.

[0029] In some embodiments, the preparation method of the anti-corrosion coating includes: uniformly mixing the mass parts of polyetheramine-modified epoxy resin, gallic blue-boron nitride hybrid material and solvent to form a suspension, and then uniformly mixing the mass parts of the first polyetheramine with the suspension to form the anti-corrosion coating.

[0030] The fifth object of the present invention is to provide an anti-corrosion coating, which includes the cured product of the anti-corrosion coating described in any of the above technical solutions.

[0031] In some embodiments, the anti-corrosion coating is suitable for substrates including, but not limited to, steel, aluminum, copper-nickel alloys, and magnesium alloys. The gallic blue in the anti-corrosion coating provides excellent protection against these substrates and, combined with the excellent dispersion of h-BN, synergistically enhances the barrier properties of the coating.

[0032] In some embodiments, the thickness of the anti-corrosion coating is 50-100 μm, and the coating within this thickness range can achieve good anti-corrosion effect.

[0033] In some embodiments, the method for forming the anti-corrosion coating includes: applying the anti-corrosion coating on a substrate, allowing it to stand for 1 to 1.5 hours for pre-curing, and then curing it at a temperature of 60 to 100° C. for 24 to 48 hours.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects:

[0035] (1) The present invention uses a gallic blue-assisted ball milling method to achieve h-BN exfoliation, which can obtain hexagonal boron nitride sheet materials with good dispersion effect, solving the problem that h-BN is easy to stack and difficult to disperse in resin;

[0036] (2) The gallic blue-boron nitride hybrid material provided by the present invention can be dispersed in a resin to form a coating with excellent barrier properties. The excellent barrier properties are derived from the good dispersibility of h-BN in the resin. On the other hand, gallic blue can also act as a corrosion inhibitor, producing a protective effect on the substrate and further improving the corrosion resistance of the coating.

[0037] (3) The anti-corrosion coating provided by the present invention can still achieve a low-frequency impedance of 10 after being immersed in simulated seawater for 105 days. 9 Ωcm 2 , indicating that it can exert excellent and long-term anti-corrosion performance in the marine environment and is suitable for marine engineering equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in this application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0039] Figure 1 is a SEM image of the h-BN@Gallocyanine hybrid material prepared in one embodiment of the present invention;

[0040] Figure 2 is a SEM image of a cross section of an anti-corrosion coating prepared in one embodiment of the present invention;

[0041] Figure 3a 、 Figure 3b 、 Figure 3c They are respectively the Nyquist plot, Bode plot, and Bode-phase angle plot of the electrode coated with the modified waterborne epoxy resin in Comparative Example 1 immersed in 3.5 wt % NaCl for different times;

[0042] Figure 4a 、 Figure 4b 、 Figure 4c They are respectively the Nyquist plot, Bode plot, and Bode-phase angle plot of the electrode coated with h-BN / WEP in Comparative Example 2 immersed in 3.5 wt % NaCl for different times;

[0043] Figure 5a 、 5b 5c are the Nyquist plot, Bode plot, and Bode-phase angle plot of the electrode coated with h-BN@Gallocyanine / WEP in Example 1 immersed in 3.5 wt % NaCl for different times;

[0044] Figure 6 These are salt spray photographs of Q235 steel plates coated with h-BN@Gallocyanine / WEP, simply modified waterborne epoxy resin, and h-BN / WEP in Example 1, Comparative Example 1, and Comparative Example 2, after being placed in a salt spray environment for 0 days, 5 days, 11 days, and 16 days;

[0045] Figure 7 Electron microscope images of the corrosion morphology of the Q235 steel plates coated with h-BN@Gallocyanine / WEP, a simple modified waterborne epoxy resin, and h-BN / WEP in Example 1, Comparative Example 1, and Comparative Example 2 after immersion in 3.5 wt % NaCl for 105 days;

[0046] Figure 8The local electrochemical impedance spectra of the electrodes coated with h-BN@Gallocyanine / WEP coating, simply modified waterborne epoxy resin, and h-BN / WEP in Example 1, Comparative Example 1, and Comparative Example 2, immersed in 3.5 wt % NaCl for 4 h, 12 h, and 24 h;

[0047] Figure 9 Schematic diagram of exfoliating hexagonal boron nitride nanosheets using gallic blue-assisted ball milling in one embodiment of the present invention. DETAILED DESCRIPTION

[0048] The technical solutions of the present invention are described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solutions of the present invention. The specific functional details disclosed herein should not be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching those skilled in the art to employ the present invention in various ways in virtually any appropriate detailed embodiment.

[0049] Unless otherwise specified, the raw materials and reagents used in the specific embodiments of the present invention are all commercially available. Unless otherwise specified, the parts described in the specific embodiments of the present invention are uniformly divided by weight.

[0050] Example 1

[0051] This embodiment provides a method for exfoliating hexagonal boron nitride nanosheets using a gallic blue-assisted ball milling method and obtaining a gallic blue-intercalated boron nitride hybrid material. Figure 9 Schematic diagram of exfoliation of hexagonal boron nitride nanosheets using gallic blue-assisted ball milling in this embodiment.

[0052] 100 parts by mass of h-BN (hexagonal boron nitride) and 100 parts by mass of gallocyanine were mixed in 2000 parts by mass of water and then ultrasonicated for 1 hour to obtain a uniform slurry. The uniform slurry was then transferred into a stainless steel tank filled with zirconia ceramic balls, the total volume of which accounted for 2 / 3 of the volume of the stainless steel tank, and the diameter of each zirconia ceramic ball was 1.7 mm. The mixture was then ball-milled at 500 revolutions per minute for 5 hours at room temperature using a planetary ball mill. After the ball milling, the obtained mixture was centrifuged at 8000 rpm for 5 minutes. The centrifuged product was freeze-dried to remove the solvent to obtain a gallocyanine-intercalated h-BN hybrid material, designated as h-BN@Gallocyanine.

[0053] 3000 parts by mass of epoxy resin E51 and 1000 parts by mass of polyetheramine M2070 were mixed, and the mixture was mechanically stirred for 6 hours to obtain a modified waterborne epoxy resin;

[0054] 15 parts by mass of the h-BN@Gallocyanine prepared above were added to 2500 parts by mass of the modified waterborne epoxy resin prepared above, and 100 parts by mass of benzyl alcohol was added as a solvent, ultrasonically dispersed for 30 minutes, and stirred at room temperature for at least 30 minutes to obtain a uniform suspension; then 600 parts by mass of polyetheramine D230 were added to the above suspension, and stirred continuously at room temperature for 30 minutes to obtain an anti-corrosion coating; thereafter, the prepared anti-corrosion coating was transferred to a preheated vacuum oven to remove bubbles, and pre-cured for 30 minutes to obtain an h-BN@Gallocyanine / WEP resin.

[0055] Figure 1 This is the SEM image of the h-BN@Gallocyanine hybrid material prepared in Example 1. Compared with the untreated h-BN, the thickness of the h-BN@Gallocyanine hybrid material is reduced, and the stacking morphology is significantly reduced. Figure 1 A disc-like structure is presented in the sample, proving that the h-BN@Gallocyanine hybrid material was successfully prepared. Figure 2 This is an SEM image of the cross section of the coating formed by coating the h-BN@Gallocyanine / WEP resin on a Q235 electrode, showing a dense coating, indicating an excellent barrier effect.

[0056] Using a 50μm wire rod, h-BN@Gallocyanine / WEP resin was applied to a Q235 electrode to form an anti-corrosion coating. Electrochemical tests were conducted on the coated electrode to verify its corrosion resistance. The h-BN@Gallocyanine / WEP resin was sprayed evenly onto a Q235 steel plate to form an anti-corrosion coating, which was then tested. The test results are shown below.

[0057] Example 2

[0058] 100 parts by mass of h-BN and 100 parts by mass of gallocyanine were mixed in 2000 parts by mass of water and then ultrasonicated for 1 hour to obtain a uniform slurry. The uniform slurry was then transferred into a stainless steel tank filled with zirconia ceramic balls, the total volume of which accounted for 2 / 3 of the volume of the stainless steel tank, and the diameter of each zirconia ceramic ball was 1.6 mm. The mixture was then ball-milled at 800 revolutions per minute for 8 hours at room temperature using a planetary ball mill. After the ball milling, the obtained mixture was centrifuged at 8000 rpm for 5 minutes. The centrifuged product was freeze-dried to remove the solvent to obtain a gallocyanine-intercalated h-BN hybrid material, designated as h-BN@Gallocyanine.

[0059] 4000 parts by mass of epoxy resin E51 and 1000 parts by mass of polyetheramine M2070 were mixed, and the mixture was mechanically stirred for 6 hours to obtain a modified waterborne epoxy resin;

[0060] 20 parts by mass of the h-BN@Gallocyanine prepared above were added to 3000 parts by mass of the modified waterborne epoxy resin prepared above, and 100 parts of xylene were added as a solvent, ultrasonically dispersed for 30 minutes, and stirred at room temperature for at least 30 minutes to obtain a uniform suspension; then 1000 parts by mass of polyetheramine D230 were added to the above suspension, and stirred continuously at room temperature for 30 minutes to obtain an anti-corrosion coating; thereafter, the prepared anti-corrosion coating was transferred to a preheated vacuum oven to remove bubbles, and pre-cured for 30 minutes to obtain h-BN@Gallocyanine / WEP resin.

[0061] Example 3

[0062] 100 parts by mass of h-BN and 150 parts by mass of gallocyanine were mixed in 2000 parts by mass of water and then ultrasonicated for 1 hour to obtain a uniform slurry. The uniform slurry was then transferred into a stainless steel tank filled with zirconia ceramic balls, the total volume of which accounted for 2 / 3 of the volume of the stainless steel tank. The diameter of each zirconia ceramic ball was 1.8 mm. The mixture was then ball-milled at 700 revolutions per minute in a planetary ball mill at room temperature for 6 hours. After the ball milling, the obtained mixture was centrifuged at 8000 rpm for 5 minutes. The centrifuged product was freeze-dried to remove the solvent to obtain a gallocyanine-intercalated h-BN hybrid material, designated as h-BN@Gallocyanine.

[0063] 350 parts by mass of epoxy resin E51 and 100 parts by mass of polyetheramine M2070 were mixed, and the mixture was mechanically stirred for 6 hours to obtain a modified waterborne epoxy resin;

[0064] 17.5 parts by mass of the h-BN@Gallocyanine prepared above were added to 2750 parts by mass of the modified waterborne epoxy resin prepared above, and 100 parts by mass of benzyl alcohol was added as a solvent, ultrasonically dispersed for 30 minutes, and stirred at room temperature for at least 30 minutes to obtain a uniform suspension; then 800 parts by mass of polyetheramine D230 were added to the above suspension, and stirred continuously at room temperature for 30 minutes to obtain an anti-corrosion coating; thereafter, the prepared anti-corrosion coating was transferred to a preheated vacuum oven to remove bubbles, and pre-cured for 30 minutes to obtain an h-BN@Gallocyanine / WEP resin.

[0065] Comparative Example 1

[0066] The only difference between Comparative Example 1 and Example 1 is that, in Comparative Example 1, a simple modified water-based epoxy resin is debubbled and then applied to a Q235 electrode using a 50 μm wire rod to form a coating, and the modified water-based epoxy resin is the same as that in Example 1; and the modified water-based epoxy resin is sprayed onto a Q235 steel plate using the same spraying method as in Example 1 to form a coating, and the following anti-corrosion performance test is performed.

[0067] Comparative Example 2

[0068] Comparative Example 2 differs from Example 1 only in that h-BN@Gallocyanine is replaced with h-BN without gallocyanine intercalation in the preparation of the anticorrosion coating. The remaining procedures are the same as in Example 1. The h-BN-based coating is applied to a Q235 electrode to form a coating. The h-BN-based coating is then sprayed onto a Q235 steel plate using the same spraying method as in Example 1 to form a coating, designated h-BN / WEP. The anticorrosion performance of the coating is then tested as follows.

[0069] Comparative Example 3

[0070] The only difference between Comparative Example 3 and Example 1 is that the gallic blue in Example 1 is replaced by aniline trimer. The preparation method of aniline trimer is:

[0071] Add p-phenylenediamine sulfate (8.87 g) and aniline (5.56 g) to a 1M hydrochloric acid solution (500 mL) in a three-necked flask and cool to -5°C. Slowly add 150 mL of a 1M hydrochloric acid solution (13.62 g) of ammonium persulfate to the reaction flask via a dropping funnel. After the addition is complete, continue stirring and react for 1 hour. Filter the reaction product and rinse with plenty of deionized water to obtain a dark green solid product. Wash the product with a 10% ammonia solution and twice with deionized water. Finally, dry it in a vacuum drying oven at 40°C until ready for use.

[0072] The comparison showed that the gallic blue exfoliation effect was better, and the thickness of the gallic blue flakes after exfoliation decreased by nearly 10 times. TEM showed that compared with the unintercalated boron nitride, the intercalated hybrid material had better dispersion in the resin and less agglomeration. Due to the better barrier properties and the active corrosion protection of the excess gallic blue, the coating with the hybrid material has higher corrosion resistance. Its electrochemical impedance can still reach 10 after immersion for 105 days. 9 Ωcm 2 , while the unfilled resin has dropped to 10 7 Ωcm 2 Since the aniline trimer prepared in Comparative Example 3 does not have active protective properties, the coating of the present invention has better anti-corrosion performance than the coating of Comparative Example 3.

[0073] The present invention conducted the following tests on the prepared gallic blue-boron nitride hybrid material, anti-corrosion coating and coating:

[0074] (1) Electrochemical testing of the h-BN@Gallocyanine / WEP composite coating to verify its corrosion resistance: A 50 μm wire rod was used to apply the h-BN@Gallocyanine / WEP resin to an electrode to form a coating. The electrode containing the coating was immersed in 3.5 wt% NaCl and the electrochemical impedance spectroscopy was measured after immersion for 10 days, 30 days, 55 days, 80 days, and 105 days. The coatings formed using the modified waterborne epoxy resin of Comparative Example 1 and the h-BN@Gallocyanine coating prepared in Comparative Example 2 were used as controls.

[0075] Figure 3a 、 3b 3c are Nyquist plots, Bode plots, and Bode-phase angle plots of the electrode coated with the modified waterborne epoxy resin in Comparative Example 1 immersed in 3.5 wt % NaCl for different times; Figure 4a 、 4b 4c are the Nyquist plot, Bode plot, and Bode-phase angle plot of the electrode coated with h-BN / WEP in Comparative Example 2 immersed in 3.5 wt % NaCl for different times; Figure 5a 、 5b 5c and 5d are the Nyquist plots, Bode plots, and Bode-phase angle plots of the electrode coated with h-BN@Gallocyanine / WEP in Example 1 immersed in 3.5wt% NaCl for different times. Comparison of these electrochemical impedance spectroscopy graphs shows that the coating with h-BN@Gallocyanine filler has the best anti-corrosion performance. Its low-frequency impedance can still reach 10 after 105 days of immersion in simulated seawater. 9 Ωcm 2 The impedance of the coating with unintercalated original boron nitride remained at 10 after 105 days of immersion. 8 Ωcm 2 In contrast, the low-frequency impedance of the unfilled epoxy resin has dropped to 10 after 105 days of immersion. 7 Ωcm 2 This shows that the addition of boron nitride increases the barrier properties of the coating, and the intercalated boron nitride of gallocyanine significantly enhances the barrier properties of the coating. Therefore, the anti-corrosion performance of the coating based on the h-BN@Gallocyanine hybrid material is greatly improved.

[0076] (2) Salt spray testing of the h-BN@Gallocyanine / WEP composite coating to verify its long-term anticorrosion performance. The coating samples were subjected to salt spray testing in accordance with GB6458-86: h-BN@Gallocyanine / WEP resin was sprayed evenly onto a Q235 steel plate to form a coating. A 3 mm long scratch was introduced into the coating surface with a scalpel. The coated steel plate was then placed in a 5 wt% salt spray environment for several days. The modified waterborne epoxy resin of Comparative Example 1 and the h-BN@Gallocyanine coating prepared in Comparative Example 2 were used as controls.

[0077] Figure 6 The following are salt spray photos of Q235 steel plates coated with h-BN@Gallocyanine / WEP coating, simple modified waterborne epoxy resin, and h-BN / WEP coating in Example 1, Comparative Example 1, and Comparative Example 2, placed in a salt spray environment for 0 days, 5 days, 11 days, and 16 days. Figure 6 It can be seen that compared with the simple modified water-based epoxy resin and h-BN / WEP coating, the h-BN@Gallocyanine / WEP coating in Example 1 did not show obvious corrosion at the scratches in a longer period of salt spray environment, and its barrier performance was better than that of the coatings in Comparative Examples 1 and 2.

[0078] (3) Electron microscope image of the corrosion morphology of the steel block surface after immersion for 105 days under the protection of the h-BN@Gallocyanine / WEP composite coating. The h-BN@Gallocyanine / WEP resin was sprayed evenly onto the Q235 steel plate to form a coating. The steel block containing the coating was immersed in 3.5wt% NaCl for 105 days, and then the epoxy AB glue encapsulating the outside of the steel block was peeled off. The corrosion morphology of the steel block surface was observed using a scanning electron microscope. The coating formed by the modified water-based epoxy resin in Comparative Example 1 and the h-BN@Gallocyanine in Comparative Example 2 were used as controls.

[0079] Figure 7Electron microscopy images of the corrosion morphology of Q235 steel plates coated with h-BN@Gallocyanine / WEP coating, a simple modified waterborne epoxy resin, and h-BN / WEP coating in Example 1, Comparative Example 1, and Comparative Example 2 after immersion in 3.5wt% NaCl for 105 days are shown. A comparison shows that the surface of the coating without filler has a large accumulation of corrosion products, indicating that the corrosive medium has reached the substrate and corrosive reactions have occurred. However, the accumulation of corrosion products is significantly reduced in the coating coated with h-BN / WEP, indicating that the addition of boron nitride has a certain effect in blocking the corrosive medium. However, the surface coated with h-BN@Gallocyanine / WEP has essentially no accumulation of corrosion products, and scratches are clearly visible when grinding, demonstrating the best corrosion protection.

[0080] (4) Local electrochemical impedance spectroscopy (EIS) testing of the h-BN@Gallocyanine / WEP composite coating to verify its dynamic protective properties. A scalpel was used to introduce a scratch approximately 2 mm long into the surface of the h-BN@Gallocyanine / WEP coating. The coating was then immersed in 3.5 wt% NaCl for varying periods of time. Coatings prepared using the modified waterborne epoxy resin of Comparative Example 1 and the h-BN@Gallocyanine prepared in Comparative Example 2 were used as controls.

[0081] Figure 8 The local electrochemical impedance spectra of electrodes coated with h-BN@Gallocyanine / WEP, a modified waterborne epoxy resin, and h-BN / WEP in Example 1, Comparative Example 1, and Comparative Example 2, after immersion in 3.5 wt% NaCl for 4, 12, and 24 hours are shown. The impedance of the unfilled epoxy coating decreases rapidly with immersion time, and the corrosion area rapidly expands along the scratch toward the surrounding area. In contrast, the corrosion of the h-BN@Gallocyanine / WEP coating expands most slowly with immersion time, and a slight upward trend in impedance at the scratch can be observed between 4 and 12 hours, indicating that the residual gallic blue molecules have good active corrosion inhibition capabilities.

[0082] The effects of the above-mentioned embodiments 2 and 3 are equivalent to those of embodiment 1.

[0083] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and are not intended to limit the present invention, the scope of which is defined solely by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0084] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0085] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions, and / or additions may be made and that substantial equivalents may be substituted for the elements of the embodiments without departing from the spirit and scope of the present invention. Additionally, many modifications may be made to adapt specific circumstances or materials to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for carrying out the present invention, but rather to include all embodiments within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. An anti-corrosion coating, characterized in that: include: 2500-3000 parts by mass of a polyetheramine-modified epoxy resin, 15-20 parts by mass of a gallic blue-boron nitride hybrid material, 600-1000 parts by mass of a first polyetheramine, and 100 parts by mass of a first solvent; The preparation method of the gallic blue-boron nitride hybrid material comprises: ball milling a mixture containing hexagonal boron nitride, gallic blue and a second solvent.

2. The anti-corrosion coating according to claim 1, characterized in that: The mass ratio of the hexagonal boron nitride to gallic blue is 1:1-1.

5.

3. The anti-corrosion coating according to claim 1, characterized in that: The ball milling process is performed at a rotation speed of 500-800 rpm for 5-8 h, and the diameter of the grinding balls used is 1.6 mm-1.8 mm.

4. The anti-corrosion coating according to claim 1, characterized in that: The preparation method further comprises performing solid-liquid separation on the product obtained by ball milling, and freeze-drying the gallic blue-boron nitride hybrid material obtained by the solid-liquid separation.

5. The anti-corrosion coating according to claim 1, characterized in that: The first polyetheramine includes one of polyetheramine D230 and polyetheramine D400, or a combination of the two.

6. The anti-corrosion coating according to claim 1, characterized in that: The first solvent includes one or a combination of multiple of benzene, toluene, xylene or propylene glycol monomethyl ether acetate.

7. The anti-corrosion coating according to claim 1, characterized in that: The raw materials of the polyetheramine-modified epoxy resin include 3000-4000 parts by mass of a base epoxy resin and 1000-1500 parts by mass of a second polyetheramine.

8. The anti-corrosion coating according to claim 7, characterized in that: The matrix epoxy resin includes one or a combination of epoxy resin E51, epoxy resin E20, and epoxy resin E44.

9. The anti-corrosion coating according to claim 7, characterized in that: The second polyetheramine includes one or a combination of polyetheramine M1000, polyetheramine M2070 or polyetheramine M600.

10. An anti-corrosion coating, characterized in that: A cured product comprising the anti-corrosion coating according to any one of claims 1 to 9.

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