Proton responsive intelligent waterborne rusted anti-rust coating and preparation method and application thereof

Abstract

The application discloses a kind of proton response type intelligent waterborne rusted antirust coating and its preparation method and application, belong to rail transit coating technical field.The coating is made of component A and component B, component A includes the following mass percentage components: waterborne epoxy resin 96%~99%, nano filler 0.5%~3%, dispersing agent 0.2%~1%, defoaming agent 0.2%~1%;Nano filler is Ti3C2T x The composite of nanosheet and DL@HMU nanoparticles is obtained by filling 3,4-dihydroxy-DL-phenylalanine in the cavity of hollow mesoporous UiO-67 nanoparticles, and then performing surface sealing with polyethyleneimine and sodium polystyrene sulfonate. Component B includes epoxy resin curing agent, curing accelerator, silane coupling agent modified aluminum tripolyphosphate, deionized water and other ingredients. The coating of the application is used for subway rail coating, which not only can inhibit stray current leakage, but also can realize the intelligent release of 3,4-dihydroxy-DL-phenylalanine, form a dense protective film, effectively block corrosion medium and play a long-acting antirust role.

Description

Technical Field

[0001] The present invention relates to the technical field of rail transit coatings, and in particular to a proton-responsive intelligent water-based rust-proof coating, and a preparation method and application thereof. Background Art

[0002] The DC traction system is used in the subway locomotive traction power supply system to transmit current to the locomotive. The system consists of a contact network, a traction substation, and rails. Due to the incomplete insulation between the rails and the ground during the actual operation of the subway, some current will leak from the rails to the ground, forming stray current. The corrosion caused by stray current is mainly manifested in the following aspects: (1) Under the interference of stray current, the rails and buried metal pipes will produce electrolysis, which accelerates corrosion and shortens their service life; (2) stray current will cause corrosion reactions on the surface of the steel bars to generate rust, destroying the structure of the steel bars, and the hydrogen generated by the reaction in the concrete cannot escape, stripping the structure between the steel bars and concrete, reducing the strength of the concrete and steel bars; (3) stray current may trigger safety accidents. Long-term leakage of stray current will cause the potential of the rails to continue to rise, threatening life safety.

[0003] To address the issue of stray current leakage in subways, resin coatings are currently the primary method of insulating subway rails. This aims to improve insulation between the rails and the ground, reduce stray current leakage, and protect the rails from corrosion. However, applying this stray current protection coating to subway rails requires rust removal from the metal surface, a labor-intensive, inefficient, and costly process. Rust removal also generates significant amounts of dust, polluting the environment. Certain inhalable particulate matter can be easily absorbed by the human body, seriously harming the health of construction workers. Therefore, there is a need for a rust-resistant coating (rust-resistant coating) that can tolerate incomplete rust removal or a small amount of rust, allowing it to be applied directly to rusted metal substrates.

[0004] Rust-resistant coatings are rust-resistant coatings that can be applied directly to metal surfaces containing rust. Their hydrolysis products form stable complexes with rust to prevent further spread of corrosion, or convert rust into stable complexes or chelates, achieving both rust prevention and protection. The amount of rust-removing agent used in reactive rust-resistant coatings is affected by the thickness of the rust, making it difficult to control. Too little rust-removing agent can lead to incomplete rust conversion, while too much can easily destabilize the paint film, affecting adhesion, water resistance, and salt spray resistance. Summary of the Invention

[0005] In order to solve the problem that the dosage of rust-removing agent in existing rust-proof coatings is difficult to control, too small a dosage will result in incomplete rust conversion, and too large a dosage will easily lead to poor coating stability, the present invention provides a proton-responsive intelligent water-based rust-proof coating.

[0006] The proton-responsive intelligent water-based rust-proof coating provided by the present invention is composed of component A and component B. Component A includes the following components in the following mass percentages:

[0007] Water-based epoxy resin 96%~99%, nano filler 0.5%~3%, dispersant 0.2%~1%, defoaming agent 0.2%~1%.

[0008] Wherein, the nanofiller is a single layer Ti3C2T x The composite of nanosheets and DL@HMU nanoparticles, wherein the DL@HMU nanoparticles are obtained by filling the cavities of hollow mesoporous UiO-67 nanoparticles with 3,4-dihydroxy-DL-phenylalanine and then sealing the pores with polyethyleneimine (PEI) and sodium polystyrene sulfonate (PSS).

[0009] The preparation method of the DL@HMU nanoparticles is as follows:

[0010] S1. The hollow mesoporous UiO-67 nanoparticles are uniformly dispersed in deionized water, 3,4-dihydroxy-DL-phenylalanine is added to fully dissolve it, and the mixture is stirred under negative pressure for 7 to 10 hours to allow the 3,4-dihydroxy-DL-phenylalanine to fully fill the cavities of the UiO-67 nanoparticles. The mixture is then centrifuged, and the precipitate is washed with deionized water and dried. The obtained product is referred to as DL@UiO-67 nanoparticles.

[0011] S2. Add DL@UiO-67 nanoparticles to a polyethyleneimine aqueous solution, stir for 30-50 minutes, then centrifuge and dry the precipitate to obtain polyethyleneimine-coated DL@UiO-67 nanoparticles, referred to as DL@UiO-67@PEI nanoparticles; add DL@UiO-67@PEI nanoparticles to a sodium polystyrene sulfonate aqueous solution, stir for 30-50 minutes, centrifuge and dry the precipitate to obtain polyethyleneimine and sodium polystyrene sulfonate-sealed DL@UiO-67 nanoparticles with a particle size of 100-300 nm, referred to as DL@HMU nanoparticles.

[0012] Preferably, in step S1, the mass ratio of the hollow mesoporous UiO-67 nanoparticles to 3,4-dihydroxy-DL-phenylalanine is 1:2.

[0013] Preferably, in step S2, the mass ratio of DL@UiO-67 nanoparticles, polyethyleneimine, and sodium polystyrene sulfonate is 10:3:3.

[0014] The preparation method of the nanofiller is as follows: a single layer of Ti3C2T xThe nanosheets were uniformly dispersed in deionized water, and then DL@HMU nanoparticles were added and stirred for 1–3 h. The mixture was centrifuged and the precipitate was dried to obtain the nanofiller.

[0015] The DL@HMU nanoparticles are combined with a single-layer Ti3C2T x Nanosheets have a significant tendency to agglomerate. If single-layer Ti3C2Tx and DL@HMU nanoparticles are directly added to epoxy resin, agglomeration will occur, thereby introducing new defects in the coating. x Nanosheets are composited to make DL@HMU nanoparticles loaded on a single layer of Ti3C2T x The surface of the nanosheet avoids the interaction between DL@HMU nanoparticles and the monolayer Ti3C2T x The agglomeration effect of nanosheets. The prepared nanofiller retains the single layer Ti3C2T x The two-dimensional nanosheet structure of the nanosheets can improve the long-term anti-corrosion performance of water-based epoxy resin coatings.

[0016] Preferably, a single layer of Ti3C2T x The lateral size of the nanosheet is 5~10μm, and the single layer Ti3C2T x The mass ratio of nanosheets to DL@HMU nanoparticles was 1:2.

[0017] Preferably, the water-based epoxy resin is selected from one of water-based epoxy emulsion H145, epoxy resin H190, and water-soluble epoxy resin H1150.

[0018] Preferably, the dispersant is ANTI-TERRA-210 or ANTI-TERRA-250.

[0019] Preferably, the defoaming agent is one of BYK-025, BYK-028 and BYK-044 produced by BYK of Germany.

[0020] The component B includes the following ingredients in percentage by mass:

[0021] Epoxy resin curing agent 50%~70%, curing accelerator 2%~5%, silane coupling agent modified aluminum tripolyphosphate 3%~7%, deionized water 20%~40%.

[0022] Preferably, the epoxy resin curing agent is selected from one of H202B, H203B, and H205B. The curing accelerator is D0590 or DMP-30.

[0023] The aluminum tripolyphosphate is surface-modified using the silane coupling agent KH550. The modification method is as follows: dissolve the silane coupling agent KH550 in deionized water, add anhydrous ethanol, then add the aluminum tripolyphosphate, stir evenly, and continue stirring at 80°C for 24 hours. Finally, the product is washed 2-3 times with deionized water and vacuum-dried to obtain KH550-modified aluminum tripolyphosphate. Modification with the silane coupling agent can improve the dispersibility and compatibility of aluminum tripolyphosphate in waterborne epoxy resin.

[0024] The present invention also provides a method for preparing a proton-responsive intelligent water-based rust-proof coating: first, a nanofiller is added to a water-based epoxy resin, and then a dispersant and a defoamer are added, and ultrasonic dispersion is carried out at 60° C. for 30 to 60 minutes to obtain component A; aluminum tripolyphosphate modified with a silane coupling agent is dispersed in deionized water, and an epoxy resin curing agent and a curing accelerator are added to obtain component B; component A is added to component B, and the mixture is stirred evenly to obtain a proton-responsive intelligent water-based rust-proof coating.

[0025] Preferably, the mass ratio of component A to component B is (1.0-1.5):(2.0-3.0).

[0026] The proton-responsive intelligent water-based rust-proof coating of the present invention is suitable for coating rusted subway rails to suppress stray current leakage and provide corrosion protection. The coating is sprayed onto rusted subway rails and dried and cured to produce the proton-responsive intelligent water-based rust-proof coating.

[0027] Compared with the prior art, the present invention is beneficial in that:

[0028] (1) The present invention encapsulates the rust-removing agent 3,4-dihydroxy-DL-phenylalanine in the cavity of hollow mesoporous UiO-67 nanoparticles. The hollow mesoporous UiO-67 has a hollow area inside, which can be filled with a large amount of 3,4-dihydroxy-DL-phenylalanine. It has an adjustable pore size, a high specific surface area, and stable properties. The specific surface area of ​​hollow mesoporous UiO-67 is 2 to 10 times that of other mesoporous materials (such as mesoporous SiO2, mesoporous TiO2, etc.). Its ultra-high specific surface area can maximize the filling of the rust-removing agent. On the other hand, the benzene ring and carboxyl group in the UiO-67 ligand can undergo π-π stacking or weak coordination with the metal Fe surface, enhancing interfacial adhesion; the oxygen atoms exposed at the metal nodes of UiO-67 (such as carboxylic acid oxygen) can form hydrogen bonds or coordination bonds on the metal Fe surface, improving the interfacial bonding between the coating and the metal substrate.

[0029] (2) The encapsulation of 3,4-dihydroxy-DL-phenylalanine in hollow mesoporous UiO-67 avoids the problems of poor film stability, film adhesion, salt spray resistance, and other performance degradation caused by excessive direct addition of 3,4-dihydroxy-DL-phenylalanine to the resin coating. The surface sealing treatment of the polyelectrolyte layer PEI / PSS realizes the intelligent release of 3,4-dihydroxy-DL-phenylalanine by DL@HMU nanoparticles. When the interface between the coating and the metal substrate corrodes, the local proton concentration at the interface changes. The PEI / PSS sealing layer has proton response characteristics. It can self-hydrolyze and structurally rupture in both weakly acidic and weakly alkaline environments, exposing the nanopores of the hollow mesoporous UiO-67, realizing the intelligent and controllable release of 3,4-dihydroxy-DL-phenylalanine.

[0030] (3) The present invention adopts Ti3C2T x / DL@HMU composite as nanofiller, Ti3C2T x / DL@HMU retains the single layer Ti3C2T x The two-dimensional nanosheet structure of the nanosheet can enhance the maze effect of the waterborne epoxy resin coating and strengthen its long-term anti-corrosion performance. On the other hand, the nanofiller Ti3C2T x / DL@HMU gives the coating the ability to intelligently identify rust. The intelligently released 3,4-dihydroxy-DL-phenylalanine can complex with rust products to form a dense protective film, effectively blocking further corrosion of the metal substrate by the corrosive medium and exerting its long-term anti-rust effect.

[0031] (4) The coating of the present invention has excellent rust prevention performance. When applied to subway rail corrosion protection, it can tolerate the coating of incomplete or small amounts of rust, eliminating the need for rust removal and reducing coating costs. The coating intelligently releases the rust-removing agent based on proton response, while meeting the requirements for subway rail resistance to stray current leakage and long-term corrosion protection. Furthermore, the coating does not contain organic solvents and is environmentally friendly.

[0032] Other advantages, objectives and features of the present invention will be reflected in part from the following description and will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram of the structure of the DL@HMU complex prepared in Example 1.

[0034] Figure 2 TEM image of the DL@HMU composite prepared in Example 1.

[0035] Figure 3 This is a schematic structural diagram of the proton-responsive intelligent water-based rust-proof coating of Example 1.

[0036] Figure 4 Schematic diagram of the intelligent release mechanism of 3,4-dihydroxy-DL-phenylalanine in the proton-responsive intelligent water-based rust-proof coating of the present invention. DETAILED DESCRIPTION

[0037] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0038] Example 1

[0039] A proton-responsive intelligent water-based rust-proof paint, the preparation steps are as follows:

[0040] S1. 0.5 g of hollow mesoporous UiO-67 nanoparticles were uniformly dispersed in 120 mL of deionized water, and 1.0 g of 3,4-dihydroxy-DL-phenylalanine was added to fully dissolve it. The above solution was placed in a -0.08 MPa environment and stirred for 8 h. The precipitate was then collected by centrifugation, washed with deionized water, and dried to obtain DL@UiO-67 nanoparticles.

[0041] S2. 0.5 g of DL@UiO-67 nanoparticles were uniformly dispersed in 50 mL of a 3 mg / mL polyethyleneimine (PEI) aqueous solution, stirred thoroughly for 30 min, and centrifuged to obtain the precipitate, which was the PEI-coated DL@UiO-67 nanoparticles, referred to as DL@UiO-67@PEI. DL@UiO-67@PEI was uniformly dispersed in 50 mL of a 3 mg / mL sodium polystyrene sulfonate (PSS) aqueous solution, stirred thoroughly for 30 min, centrifuged, and the precipitate was dried to obtain DL@UiO-67 with surface PEI / PSS sealing (DL@UiO-67@(PEI / PSS)), referred to as DL@HMU nanoparticles. The structure of DL@HMU nanoparticles is shown in Figure 1 , TEM images are shown in Figure 2 ,Depend on Figure 2 It can be seen that the cavity of UiO-67 nanoparticles is filled with 3,4-dihydroxy-DL-phenylalanine and the structure is intact after PEI / PSS surface sealing treatment, and it still maintains its unique octahedral structure; this is because UiO-67 has good chemical stability and can maintain its structural integrity in water, various organic solvents and certain acidic and alkaline conditions.

[0042] S3, single layer Ti3C2T x Nanosheets are dispersed in deionized water, Ti3C2T x The concentration of nanosheets was 2 mg / mL; then 50 mL of single-layer Ti3C2T xThe water phase dispersion liquid was added with 0.2 g of the Ti3C2T / DL@HMU composite, i.e. the nano filler, and stirred for 2 h, centrifuged and separated, and the precipitate was dried to obtain the Ti3C2T / DL@HMU composite. x / DL@HMU composite, i.e. the nano filler.

[0043] S4, 0.05 g of the Ti3C2T / DL@HMU composite was added into 10 g of the epoxy resin H190, and then 0.05 g of the dispersant ANTI-TERRA-210 and 0.05 g of the defoaming agent BYK-028 were added, and ultrasonic dispersion was performed at 60 DEG C for 60 min to obtain component A. x

[0044] S5, 1 g of the silane coupling agent KH550 modified aluminum tripolyphosphate was dispersed in 8 g of deionized water, and 0.7 g of the curing accelerator D0590 and 15 g of the water-based epoxy curing agent H203B were added to obtain component B. The method for modifying the aluminum tripolyphosphate with the silane coupling agent KH550 is as follows: first, 5 g of the silane coupling agent KH550 was dissolved in 20 g of deionized water, and then 50 g of anhydrous ethanol was added; subsequently, 1 g of the aluminum tripolyphosphate was added and uniformly dispersed by stirring; the mixture was placed on a constant-temperature magnetic stirrer and stirred at 80 DEG C for 24 h; finally, the product was washed 2-3 times with deionized water and vacuum dried to obtain the KH550 modified aluminum tripolyphosphate.

[0045] S6, component A was added into component B and mixed uniformly to obtain the proton response type intelligent water-based rusted anti-rust coating.

[0046] The prepared coating was sprayed on the surface of the subway rail steel U71Mn using a spray gun, and cured at room temperature to obtain the proton response type intelligent water-based rusted anti-rust coating layer, and the coating structure is shown in Figure 3 .

[0047] Example 2

[0048] On the basis of Example 1, the addition amount of the nano filler Ti3C2T / DL@HMU composite was adjusted to 0.1 g, accounting for 1% of the mass percentage of the water-based epoxy resin in component A. x

[0049] Example 3

[0050] On the basis of Example 1, the addition amount of the nano filler Ti3C2T / DL@HMU composite was adjusted to 0.15 g, accounting for 1.5% of the mass percentage of the water-based epoxy resin in component A. x

[0051] Example 4

[0052] On the basis of Example 1, the addition amount of the nano filler Ti3C2T / DL@HMU composite was adjusted to 0.15 g, accounting for 1.5% of the mass percentage of the water-based epoxy resin in component A. x ​​​The amount of the added DL@HMU compound was adjusted to 0.2 g, accounting for 2% of the mass percentage of the waterborne epoxy resin in component A.

[0053] Comparative Example 1

[0054] On the basis of Example 1, in step S4, no nano-filler Ti3C2T was added to component A. x DL@HMU compound.

[0055] Comparative Example 2

[0056] On the basis of Example 1, in step S2, the DL@UiO-67 nanoparticles were only surface-treated with PEI to obtain DL@UiO-67@PEI, and the DL@UiO-67@PEI was used as a nano-filler in step S3.

[0057] Comparative Example 3

[0058] On the basis of Example 1, in step S2, the DL@UiO-67 nanoparticles were directly surface-sealed with PSS without using PEI to obtain DL@UiO-67@PSS, and the DL@UiO-67@PSS was used as a nano-filler in step S3.

[0059] Comparative Example 4

[0060] On the basis of Example 1, step S2 was omitted, and the unsealed DL@UiO-67 nanoparticles were directly used as a nano-filler in step S3.

[0061] The coatings formed by Examples 1-4 and Comparative Examples 1-4 were subjected to performance tests such as corrosion resistance and adhesion. The performance test items and standards involved are as follows:

[0062] Corrosion resistance of the coating: GB / T 9274-1988 “Liquid Medium Resistance of Color Paint and Varnish”.

[0063] Adhesion: GB / T 5210-2006 “Color Paint and Varnish Adhesion Test by Pulling Method”.

[0064] Neutral salt spray: GB / T 1771-2007 “Determination of the Resistance of Color Paint and Varnish to Neutral Salt Spray”.

[0065] The performance test results are shown in Table 1.

[0066] Table 1, corrosion resistance, adhesion, and neutral salt spray test results of the coatings formed by Examples 1-4 and Comparative Examples 1-4

[0067]

[0068] By comparing Examples 1 to 4 with Comparative Examples 1 to 4, it can be found that the nanofiller Ti3C2T x The addition of Ti3C2T / DL@HMU composite significantly improves the anti-corrosion and anti-rust properties of the prepared coating. x / DL@HMU composites maintain the two-dimensional Ti3C2T x The layered structure of the nanosheets improves the anti-corrosion performance of the coating. After 2000 hours of neutral salt spray, the substrate corrosion area of ​​Comparative Example 1 reached 20%, while Examples 1 to 4 had lower substrate corrosion areas, and the substrate corrosion area increased with the increase of the nanofiller Ti3C2T x / DL@HMU composites with the increase of the addition amount. This is because, Figure 4 As shown, the DL@HMU composite is coated with proton-responsive PEI / PSS. When corrosion occurs at the coating / metal substrate interface, the local proton concentration changes, causing the PEI / PSS coating to decompose, exposing the hollow mesoporous UiO-67 nanochannels and enabling the intelligent release of 3,4-dihydroxy-DL-phenylalanine encapsulated within them. 3,4-dihydroxy-DL-phenylalanine possesses a catechol, amino, and carboxyl structure. These phenolic hydroxyl, amino, and carboxyl groups possess strong chelating and adsorption abilities, allowing them to undergo physical and chemical adsorption on the Fe surface, forming a dense, insoluble complex film. This effectively blocks further corrosion of the metal substrate by the corrosive medium, exerting its long-lasting rust-preventing effect. When DL@UiO-67 nanoparticles are surface-sealed solely with PEI, the pores of the UiO-67 nanoparticles are incompletely sealed. PEI, a positively charged cationic polyelectrolyte, can electrostatically adsorb to the negatively charged UiO-67 surface. However, its highly flexible molecular chains and wide size distribution make it difficult to form a tight sealing layer, and the pores may remain partially exposed. Furthermore, in dispersion media such as water, the PEI chains may swell or desorb, leading to sealing failure and accelerating the sudden release of the loaded molecules. This makes it difficult for the coating to exhibit proton-responsive properties, and its long-term rust prevention performance will fall short of expectations. When DL@UiO-67 nanoparticles are surface-sealed solely with PSS, PSS, a negatively charged anionic polyelectrolyte, electrostatically repel the negatively charged UiO-67 surface, making it difficult to directly adsorb and form a film, failing to cover the UiO-67 pores. Without any surface treatment, the coating lacks proton-responsive intelligent properties.

[0069] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A proton-responsive intelligent water-based rust-proof paint, characterized in that: It is composed of component A and component B, wherein component A includes the following components in percentage by mass: Waterborne epoxy resin 96%~99%, nano filler 0.5%~3%, dispersant 0.2%~1%, defoamer 0.2%~1%; The nanofiller is a single layer Ti3C2T x A composite of nanosheets and DL@HMU nanoparticles, wherein the DL@HMU nanoparticles are obtained by filling the cavities of hollow mesoporous UiO-67 nanoparticles with 3,4-dihydroxy-DL-phenylalanine and then sealing the pores with polyethyleneimine and sodium polystyrene sulfonate; The component B includes the following ingredients in percentage by mass: Epoxy resin curing agent 50%~70%, curing accelerator 2%~5%, silane coupling agent modified aluminum tripolyphosphate 3%~7%, deionized water 20%~40%.

2. The proton-responsive intelligent water-based rust-proof paint according to claim 1, characterized in that: The preparation method of the DL@HMU nanoparticles is as follows: S1. The hollow mesoporous UiO-67 nanoparticles are uniformly dispersed in deionized water, 3,4-dihydroxy-DL-phenylalanine is added to fully dissolve it, and the mixture is stirred under negative pressure for 7 to 10 hours to allow the 3,4-dihydroxy-DL-phenylalanine to fully fill the cavities of the UiO-67 nanoparticles. The mixture is then centrifuged, washed with deionized water, and dried. The obtained product is referred to as DL@UiO-67 nanoparticles. S2. Add DL@UiO-67 nanoparticles to a polyethyleneimine aqueous solution, stir for 30-50 min, then centrifuge and dry the precipitate to obtain polyethyleneimine-coated DL@UiO-67 nanoparticles, referred to as DL@UiO-67@PEI nanoparticles; add DL@UiO-67@PEI nanoparticles to a sodium polystyrene sulfonate aqueous solution, stir for 30-50 min, centrifuge and dry the precipitate to obtain polyethyleneimine and sodium polystyrene sulfonate-sealed DL@UiO-67 nanoparticles, referred to as DL@HMU nanoparticles.

3. The proton-responsive intelligent water-based rust-proof paint according to claim 2, characterized in that: In step S1, the mass ratio of hollow mesoporous UiO-67 nanoparticles to 3,4-dihydroxy-DL-phenylalanine is 1:

2.

4. The proton-responsive intelligent water-based rust-proof paint according to claim 2, characterized in that: In step S2, the mass ratio of DL@UiO-67 nanoparticles, polyethyleneimine, and sodium polystyrene sulfonate is 10:3:

3.

5. The proton-responsive intelligent water-based rust-proof paint according to claim 2, characterized in that: The preparation method of the nanofiller is as follows: a single layer of Ti3C2T x The nanosheets were uniformly dispersed in deionized water, and then DL@HMU nanoparticles were added and stirred for 1–3 h. The mixture was centrifuged and the precipitate was dried to obtain the nanofiller.

6. The proton-responsive intelligent water-based rust-proof paint according to claim 5, characterized in that: Single-layer Ti3C2T x The mass ratio of nanosheets to DL@HMU nanoparticles was 1:

2.

7. The proton-responsive intelligent water-based rust-proof paint according to claim 1, characterized in that: The dispersant is ANTI-TERRA-210 or ANTI-TERRA-250.

8. A method for preparing a proton-responsive intelligent water-based rust-proof coating according to any one of claims 1 to 7, characterized in that: First, nanofillers are added to water-based epoxy resin, and then dispersants and defoamers are added, and ultrasonic dispersion is carried out at 60°C for 30-60 minutes to obtain component A; aluminum tripolyphosphate modified with a silane coupling agent is dispersed in deionized water, and epoxy resin curing agent and curing accelerator are added to obtain component B; component A is added to component B, and the mixture is stirred evenly to obtain a proton-responsive intelligent water-based rust-proof coating.

9. The method for preparing the proton-responsive intelligent water-based rust-proof paint according to claim 8, wherein: The mass ratio of component A to component B is (1.0~-1.5): (2.0~3.0).

10. An application of the proton-responsive intelligent water-based rust-proof coating according to any one of claims 1 to 7, characterized in that: Coating of subway rails to suppress stray current leakage and provide corrosion protection.

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