Recyclable construct-deconstruct antimicrobial micro-interface s 2- Response corrosion protection coating preparation method

Abstract

The application discloses a recyclable construction-deconstruction antibacterial micro-interface S 2‑ The application discloses a preparation method of a response anti-corrosion coating, which comprises the following steps: preparing a copper-containing metal organic framework HKUST-1; modifying the HKUST-1 by using ethylenediaminetetraacetic acid to obtain E-HKUST-1; preparing core-shell PMMA grafted chitosan copolymer E-HKUST-1 microspheres (PCEH-1) by using the E-HKUST-1 as a polymerization site and through a solution polymerization method; preparing a solid phase and a liquid phase of a sprayable anti-corrosion coating; and high-pressure spraying the solid phase and the liquid phase after mixing and stirring the solid phase and the liquid phase into a fluid with a concentration of 1-2 g / mL to obtain the anti-corrosion coating. The coating prepared by the method has the characteristics of recyclable construction-deconstruction antibacterial micro-interface and long-term stable anti-corrosion effect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metal anticorrosion coating preparation methods, and particularly relates to a S 2- responsive anticorrosion coating preparation method. BACKGROUND

[0002] Bacteria can cause pitting corrosion, crevice corrosion and the like on alloy surfaces through metabolic products and biofilm formation. In the field of electric power engineering, sulfate-reducing bacteria corrosion is one of the main factors leading to the failure of underground cable signal transmission. The shielding layer and armor of the power transmission system cable are mostly alloy materials. After the alloy shielding layer is corroded, the electromagnetic shielding ability decreases, affecting signal transmission, and the mechanical strength of the metal decreases, making the cable more prone to breakage due to external forces during laying and use. The insulation layer is eroded by sulfate-reducing bacteria, and the insulation performance deteriorates rapidly, causing electric leakage, short circuit, leading to power transmission interruption, and affecting power supply stability. In addition, continuous sulfate-reducing bacteria erosion accelerates cable aging, shortens service life, increases maintenance costs and safety hazards, and brings huge losses to the power system.

[0003] The S 2- responsive ion release type anticorrosion coating is a typical representative of the new generation of alloy anticorrosion materials, which has the ability to actively recognize sulfate-reducing bacteria and their metabolic products. By sensing specific chemical reactions or physical changes, the ion release concentration is dynamically regulated according to the actual conditions of the complex and variable environment, which has a significant inhibitory effect on the growth of sulfate-reducing bacteria, effectively preventing bacterial corrosion. Compared with traditional anticorrosion coatings, S 2- responsive anticorrosion coatings exhibit more outstanding performance, however, the existing S 2- responsive anticorrosion coatings have the problem of continuous leakage of antibacterial substances after response, which not only has a negative impact on the long-term stability of the anticorrosion performance of the coating, but also may have potential ecological risks to the surrounding soil and water environment.

[0004] Chinese patent "A corrosion-resistant filler with intelligent response and its preparation method and application" (application number: 202310316576.8, publication date: 2024.01.23, publication number: CN116285463B) discloses a corrosion-resistant filler with intelligent response and its preparation method and application. Chinese patent "Intelligent response self-repairing corrosion-resistant coating material and preparation method" (application number: 201910365017.X, publication date: 2019.08.02, publication number: CN110079140A) discloses an intelligent response self-repairing corrosion-resistant coating material and a preparation method. The intelligent response corrosion-resistant materials disclosed in the two patents will accelerate the release of corrosion inhibitors when the environmental pH value is acidic, delaying corrosion. However, once the environment changes, the corrosion inhibitors will continue to leak, negatively affecting the long-term corrosion resistance of the coating, and potentially posing ecological risks to the surrounding soil and water environment.

[0005] Obviously, it is of great significance to develop other new environmentally responsive corrosion-resistant coatings, providing new ideas and technical support for developing more green and sustainable alloy corrosion-resistant materials. SUMMARY

[0006] The purpose of the present application is to provide a recyclable construction-deconstruction antibacterial micro-interface S 2- response corrosion-resistant coating preparation method, the coating prepared by the method has the characteristics of recyclable construction-deconstruction antibacterial micro-interface and long-term stable corrosion resistance.

[0007] The technical solution adopted by the present application is a recyclable construction-deconstruction antibacterial micro-interface S 2- response corrosion-resistant coating preparation method, which is implemented according to the following steps:

[0008] Step 1, prepare copper-containing metal organic framework HKUST-1;

[0009] Step 2, use ethylenediaminetetraacetic acid to modify the HKUST-1 obtained in step 1 to obtain E-HKUST-1;

[0010] Step 3, use E-HKUST-1 obtained in step 2 as a polymerization site to prepare core-shell polymethyl methacrylate grafted chitosan copolymer E-HKUST-1 core-shell microspheres, i.e. PCEH-1, by solution polymerization;

[0011] Step 4, prepare a solid phase of a sprayable corrosion-resistant coating;

[0012] Step 5, prepare a liquid phase of a sprayable corrosion-resistant coating;

[0013] Step 6, mix and stir the solid phase and the liquid phase prepared in steps 4 and 5 into a fluid with a concentration of 1-2 g / mL, and then high-pressure spray to obtain the corrosion-resistant coating.

[0014] The application also has the characteristics that:

[0015] Step 1 is specifically:

[0016] Cu(NO3)2 and trimesic acid are dissolved in N,N-dimethylformamide at a molar ratio of 0.1-0.5:1, wherein the mass fraction of Cu(NO3)2 is 1-5%; the mixed solution is reacted at 100-200°C for 12-24h to enable the metal ions and the organic ligand to self-assemble to form HKUST-1 crystals; after the reaction is completed, the product is washed with dimethylformamide and ethanol alternately for 3-5 times to remove unreacted raw materials and impurities, and then is subjected to activation treatment at 50-70°C to remove solvent molecules in the pores, and finally is vacuum dried at a temperature of 50-70°C to obtain HKUST-1.

[0017] Step 2 is specifically:

[0018] The HKUST-1 obtained in step 1 is added into an ethylenediaminetetraacetic acid solution, and is stirred at room temperature for 12-24h to enable the ethylenediaminetetraacetic acid to fully interact with the surface of the HKUST-1; then the reaction liquid is centrifuged, the precipitate is collected and washed with deionized water, and the washed product is dried in a vacuum drying oven at 60-80°C for 12-24h to obtain E-HKUST-1.

[0019] The mass fraction of the ethylenediaminetetraacetic acid solution is 1-5%; the mass ratio of HKUST-1 to ethylenediaminetetraacetic acid is 2-25:1; and the centrifugal rate is 3000-5000r / min.

[0020] Step 3 is specifically:

[0021] The chitosan solution is mixed with methyl methacrylate, and then a water-ethanol mixed solution is added; then methylene bisacrylamide and polyvinylpyrrolidone are added into the reaction system, and under the protection of an inert atmosphere, stirring is performed at 30-40°C for 30-60min; then azobisisobutyronitrile and the E-HKUST-1 obtained in step 2 are added, the temperature is raised to 70-80°C, and stirring is performed for 3-5h; and then freeze-drying is performed to obtain the core-shell microspheres PCEH-1.

[0022] The specific preparation method of the chitosan solution is as follows: chitosan is dissolved in an acetic acid aqueous solution with a mass fraction of 1-2%, and stirring is performed at room temperature until complete dissolution, wherein the mass fraction of chitosan is 1-6%; filtration is performed with a filter membrane to remove insoluble impurities, and the chitosan solution is obtained.

[0023] The mass ratio of the chitosan solution to methyl methacrylate is 0.1-1:1; and the volume ratio of water to ethanol in the water-ethanol mixed solution is 2-5:1.

[0024] The mass percentages of methylene bisacrylamide, polyvinylpyrrolidone, azobisisobutyronitrile, and E-HKUST-1 added in step 3 are 1-5%, 2-8%, 1-5%, and 1-10% of the total mass of chitosan solution and methyl methacrylate, respectively.

[0025] Step 4 is as follows:

[0026] The PCEH-1 obtained in step 3 and the initiator benzoyl peroxide (BPO) are mixed to obtain a sprayable anti-corrosion coating solid phase, wherein the mass percentage of PCEH-1 is 99.8%~99.9% and the mass percentage of BPO is 0.1%~0.2%.

[0027] Step 5 specifically involves:

[0028] The liquid phase of the sprayable anti-corrosion coating is prepared by uniformly mixing methyl methacrylate monomer, N,N-dimethyl-p-toluidine, and hydroquinone; wherein the mass percentage of methyl methacrylate monomer is 96.5-99.5%, the mass percentage of N,N-dimethyl-p-toluidine is 0.4-3%, and the mass percentage of hydroquinone is 0.1-0.5%.

[0029] The beneficial effects of this invention are:

[0030] (1) The core-shell microspheres in the anti-corrosion coating of the present invention are formed through a self-polymerization reaction, and the core material E-HKUST-1 is effective against the metabolic products S of underground corrosion bacteria (sulfate-reducing bacteria). 2- It possesses highly accurate response characteristics. 2- Destroying the organic ligand pyromellitic acid and Cu 2+ Intercoordinate bonds trigger dissociation and promote Cu 2+ Continuing to diffuse outwards, the outer layer of chitosan molecules, rich in amino and hydroxyl groups, interacts with Cu through electrostatic and coordination interactions. 2+ Recombining with each other, at the microscopic level Cu 2+ Fixed to the surface of microspheres, the micro-interface macroscopically forms an antibacterial micro-interface in the coating-soil contact area. The constructed antibacterial micro-interface significantly inhibits the growth of sulfate-reducing bacteria on the coating surface, effectively preventing bacterial corrosion; furthermore, the antibacterial micro-interface effectively prevents the coating from being affected by sulfate-reducing bacteria. 2- The continuous release of antibacterial substances after response ensures the long-term anti-corrosion performance of the coating while reducing potential risks to the ecological environment.

[0031] (2) The method of this invention relies on the difference in coordination ability of different ligands to antibacterial ions, and uses the ligand competition mechanism to realize the dynamic cyclic construction and deconstruction of responsive antibacterial micro-interfaces within the coating system, specifically as follows:

[0032] The death of sulfate-reducing bacteria led to S 2-After the signal disappears, the dissociation process of E-HKUST-1 is terminated, and the antibacterial micro-interface construction is completed. Subsequently, according to the coordination competition principle, the surface modification of E-HKUST-1 with EDTA with strong coordination competition ability will make Cu 2+ from the chitosan molecule and re-chelate to E-HKUST-1, resulting in the deconstruction of the antibacterial micro-interface. Once S 2- The signal appears again, and the decoordination process of E-HKUST-1 is reactivated, and the antibacterial micro-interface is formed again.

[0033] This dynamic cycle construction process is not a simple periodic change, but a self-response call and re-storage of the antibacterial and anticorrosive substance based on the microstructure and chemical composition of the material to the external signal stimulus, which ensures the efficiency and permanent effectiveness of the coating in maintaining the anticorrosive function.

[0034] (3) The S 2- The underground anticorrosive coating with long-term stable green anticorrosive effect and the ability to construct and deconstruct the antibacterial micro-interface in response to the cycle. In the field of metal corrosion protection, the coating technology is expected to break through the limitations of traditional corrosion protection methods and provide a new, efficient and green solution for the protection of underground metal facilities, which has broad application prospects and significant economic and social benefits. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is the agar plate coating colony detection result graph of the coating prepared by the method of the present application. DETAILED DESCRIPTION

[0036] The present application will be described in detail below in combination with the drawings and specific embodiments.

[0037] The S 2- The preparation method of the corrosion-resistant coating in response to the cycle is implemented according to the following steps:

[0038] Step 1, preparation of copper-containing metal organic framework (HKUST-1)

[0039] Copper nitrate (Cu(NO3)2) is selected as a metal source, and benzene-1,3,5-tricarboxylic acid (BTC) is selected as an organic ligand to prepare MOF (HKUST-1) with specific pore structure and metal active sites. Cu(NO3)2 and BTC are dissolved in N,N-dimethylformamide (DMF) at a molar ratio of 0.1-0.5:1, and the mass fraction of Cu(NO3)2 is 1-5%; the mixed solution is transferred to a reaction kettle, and the metal ions and organic ligands are self-assembled to form HKUST-1 crystals at 100-200℃ for 12-24h. After the reaction, the product is washed with DMF and ethanol alternately for 3-5 times to remove unreacted raw materials and impurities. Then, the product is activated at 50-70℃ to remove solvent molecules in the pores, and finally, the product is dried at 50-70℃ under vacuum to obtain HKUST-1;

[0040] Step 2, preparation of EDTA surface-modified HKUST-1 (E-HKUST-1)

[0041] EDTA is dissolved in deionized water and ultrasonically treated for 15-30min to completely dissolve the EDTA, obtaining an EDTA solution with a mass fraction of 1-5%. HKUST-1 crystals obtained in step 1 are weighed, and the mass ratio of HKUST-1 crystals to EDTA is 2-25:1. The HKUST-1 crystals are added to the EDTA solution, and the mixture is stirred at room temperature for 12-24h to allow EDTA to fully interact with the surface of HKUST-1. After stirring, the mixture is transferred to a centrifuge tube and centrifuged at 3000-5000r / min to collect the precipitate. The precipitate is washed with deionized water for 3-5 times and centrifuged to remove unbound EDTA. The washed product is placed in a vacuum drying oven and dried at 60-80℃ for 12-24h to obtain EDTA surface-modified HKUST-1 (E-HKUST-1);

[0042] Step 3, preparation of PMMA grafted CS core-shell microspheres (PCEH-1) on E-HKUST-1

[0043] Dissolve chitosan in 1-2% acetic acid aqueous solution, stir at room temperature until completely dissolved, obtain chitosan solution, wherein the mass fraction of chitosan is 1-6%. Filter with filter membrane to remove insoluble impurities, obtain clear chitosan solution for standby. Mix chitosan solution (CS) and methyl methacrylate (MMA) monomer in a three-necked flask according to the mass ratio of 0.1-1:1, and add water-ethanol mixed solution in the mixed system again, the volume ratio of water to ethanol in the mixed solution is 2-5:1, then according to the total mass percentage of chitosan solution and MMA monomer, 1-5% methylene bisacrylamide (MBA) and 2-8% polyvinylpyrrolidone (PVP) are added, under the protection of inert atmosphere, stir at 30-40℃ for 30-60min, then, according to the total mass percentage of chitosan solution and MMA monomer, 1-5% azobisisobutyronitrile (AIBN) and 1-10% E-HKUST-1 are added again, heat to 70-80℃, stir for 3-5h, freeze-drying, to obtain poly methyl methacrylate (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1);

[0044] Step 4, preparation of a sprayable anticorrosive coating solid phase

[0045] Mix PCEH-1 and initiator diphenylboron peroxide BPO, wherein the mass percentage of PCEH-1 is 99.8-99.9%, and the mass percentage of BPO is 0.1-0.2%, after mixing, obtain a sprayable anticorrosive coating solid phase;

[0046] Step 5, preparation of a sprayable anticorrosive coating liquid phase

[0047] Mix methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone uniformly, to obtain a sprayable anticorrosive coating liquid phase; wherein the mass percentage of methyl methacrylate monomer is 96.5-99.5%, the mass percentage of N,N-dimethyl-p-toluidine is 0.4-3%, and the mass percentage of hydroquinone is 0.1-0.5%.

[0048] Step 6, preparation of a sprayable anticorrosive coating

[0049] After mixing and stirring the sprayable anticorrosive coating solid phase and the sprayable anticorrosive coating liquid phase into a fluid according to 1-2g / mL, high-pressure spraying can be carried out.

[0050] The application can construct-deconstruct antibacterial micro-interface S 2-The method for preparing the anti-corrosion coating comprises the following steps: firstly, a copper-containing metal organic framework (E-HKUST-1) is prepared by using self-coordination and surface modification technology; secondly, a core-shell poly methyl methacrylate (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1) are prepared by using the E-HKUST-1 as a polymerization site and by a solution polymerization method; the PCEH-1 and an initiator BPO are uniformly mixed in a certain mass ratio to obtain a solid phase of the sprayable anti-corrosion coating; MMA, N,N-dimethyl-p-toluidine and p-benzoquinone are uniformly mixed in a certain mass ratio to obtain a liquid phase of the sprayable anti-corrosion coating; and the solid phase and the liquid phase are mixed, stirred and high-pressure sprayed.

[0051] Example 1

[0052] The S of this embodiment can be recycled to construct and deconstruct the antibacterial micro-interface 2- The method for preparing the anti-corrosion coating comprises the following steps:

[0053] Step 1, preparation of a copper-containing metal organic framework (HKUST-1)

[0054] Copper nitrate (Cu(NO3)2) is selected as a metal source, and benzenetricarboxylic acid (BTC) is selected as an organic ligand to prepare the HKUST-1 with specific pore structure and metal active sites. Cu(NO3)2 and BTC are dissolved in 20 mL of N,N-dimethylformamide in a molar ratio of 0.1:1, and the mass fraction of Cu(NO3)2 is 1%. The mixed solution is transferred to a reaction kettle, and the metal ions and the organic ligand are self-assembled to form HKUST-1 crystals at 100℃ for 12 h. After the reaction is completed, the product is washed with dimethylformamide (DMF) and ethanol alternately for 3 times to remove unreacted raw materials and impurities. Then, the product is activated at 50℃ to remove solvent molecules in the pores, and finally, the product is vacuum dried to obtain the HKUST-1, and the vacuum drying temperature is 50℃;

[0055] Step 2, preparation of ethylenediaminetetraacetic acid (EDTA) surface modified HKUST-1 (E-HKUST-1)

[0056] Take 0.2 g of EDTA, dissolve it in 20 mL of deionized water, ultrasonic treatment for 15 min, make it completely dissolved, get EDTA solution. Take 5 g of HKUST-1 crystal, add it to the EDTA solution, stir at room temperature for 12 h, make EDTA fully interact with the surface of HKUST-1. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 3000 r / min, collect the precipitate. Wash the precipitate with deionized water 3 times to remove unbound EDTA. Put the washed product into a vacuum drying oven, dry at 60℃ for 12 h, get EDTA surface modified HKUST-1 (E-HKUST-1);

[0057] Step 3, preparation of poly (methyl methacrylate) (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1)

[0058] Take 2 g of chitosan, dissolve it in 100 mL of 1% mass fraction of acetic acid aqueous solution, stir at room temperature until completely dissolved, get chitosan solution. Filter with filter membrane to remove insoluble impurities, get clear chitosan solution for use. Mix the chitosan solution and methyl methacrylate (MMA) monomer in a three-necked flask according to the mass ratio of 0.1:1, the total mass is 10 g, and add water-ethanol mixed solution in the mixed system again, the addition amount of water and ethanol is 100 mL, and the volume ratio is 2:1, then according to the total mass percentage of chitosan solution and MMA monomer, add 1% methyl methacrylate (MMA), 2% polyvinylpyrrolidone (PVP), under the protection of inert atmosphere, stir at 30℃ for 30 min, then, according to the total mass percentage of chitosan solution and MMA monomer, add 1% azobisisobutyronitrile (AIBN) and 0.1 g of E-HKUST-1, heat to 70℃, stir for 3 h, freeze-dry, get poly (methyl methacrylate) (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1);

[0059] Step 4, preparation of solid phase of sprayable anticorrosive coating

[0060] Mix PCEH-1 and initiator dibenzoyl peroxide BPO, the mass percentage of PCEH-1 is 99.9%, the mass percentage of BPO is 0.1%, after mixing, get the solid phase of sprayable anticorrosive coating;

[0061] Step 5, preparation of liquid phase of sprayable anticorrosive coating

[0062] Methyl methacrylate monomer (MMA), N, N-dimethyl-p-toluidine, hydroquinone are mixed uniformly, which is a sprayable anticorrosive coating liquid phase; the mass percentages of the three are 96.5%, 3% and 0.5% respectively.

[0063] Step 6, preparation of a sprayable anticorrosive coating

[0064] After the sprayable anticorrosive coating solid phase and the sprayable anticorrosive coating liquid phase are mixed and stirred into a fluid at 1 g / mL, high-pressure spraying can be performed.

[0065] Example 2:

[0066] This example can construct and deconstruct the S of the antibacterial micro-interface 2- In response to the preparation method of the anticorrosive coating, the following steps are implemented in detail:

[0067] Step 1, preparation of copper-containing metal organic framework (HKUST-1)

[0068] Copper nitrate (Cu(NO3)2) is selected as the metal source, and benzene-1, 3, 5-tricarboxylic acid (BTC) is selected as the organic ligand to prepare HKUST-1 with specific pore structure and metal active sites. Cu(NO3)2 and BTC are dissolved in 20 mL of N, N-dimethylformamide at a molar ratio of 0.2:1, and the mass fraction of Cu(NO3)2 is 2%. The mixed solution is transferred to a reaction kettle and reacted at 200℃ for 12h, so that the metal ions and the organic ligand self-assemble to form HKUST-1 crystals. After the reaction is completed, the product is washed with dimethylformamide (DMF) and ethanol alternately for 5 times to remove unreacted raw materials and impurities. Then, activation treatment is carried out at 65℃ to remove the solvent molecules in the pores, and finally vacuum drying is carried out to obtain HKUST-1, and the vacuum drying temperature is 60℃;

[0069] Step 2, preparation of ethylenediaminetetraacetic acid (EDTA) surface modified HKUST-1 (E-HKUST-1)

[0070] 0.5g of EDTA is weighed and dissolved in 50mL of deionized water, and ultrasonic treatment is carried out for 30min to make it completely dissolved to obtain an EDTA solution. 7.5g of HKUST-1 crystals is weighed and added to the EDTA solution, and magnetic stirring is carried out at room temperature for 24h to make EDTA fully interact with the surface of HKUST-1. After stirring, the mixed solution is transferred to a centrifugal tube and centrifuged at 5000r / min to collect the precipitate. The precipitate is washed with deionized water for 5 times to remove unbound EDTA. The washed product is placed in a vacuum drying oven and dried at 80℃ for 24h to obtain EDTA surface modified HKUST-1 (E-HKUST-1);

[0071] Step 3, preparation of poly(methyl methacrylate) (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1)

[0072] Weigh 3g of chitosan, dissolve it in 100mL of 1% mass fraction of aqueous acetic acid solution, stir at room temperature until completely dissolved, to obtain a chitosan solution. Filter with filter membrane to remove insoluble impurities, to obtain a clear chitosan solution for use. Mix the chitosan solution and methyl methacrylate (MMA) monomer in a three-necked flask according to the mass ratio of 0.5:1, the total mass is 10g, and add water-ethanol mixed solution in the mixed system again, the amount of water and ethanol added is 100mL, and the volume ratio is 5:1, then according to the total mass percentage of chitosan solution and MMA monomer, 2% methyl methacrylate (MMA), 4% polyvinylpyrrolidone (PVP) is added, under the protection of inert atmosphere, stirring at 40℃ for 40min, then, according to the total mass percentage of chitosan solution and MMA monomer, 5% azobisisobutyronitrile (AIBN) and 0.4g of E-HKUST-1 are added, heated to 75℃, stirred for 5h, and freeze-dried to obtain poly(methyl methacrylate) (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1);

[0073] Step 4, preparation of a solid phase of a sprayable anticorrosive coating

[0074] Mix PCEH-1 and initiator dibenzoyl peroxide BPO, wherein the mass percentage of PCEH-1 is 99.8% and the mass percentage of BPO is 0.2%, to obtain a solid phase of a sprayable anticorrosive coating after mixing;

[0075] Step 5, preparation of a liquid phase of a sprayable anticorrosive coating

[0076] Mix methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine, and hydroquinone uniformly to obtain a liquid phase of a sprayable anticorrosive coating; the mass percentages of the three are 97.5%, 2% and 0.5% respectively.

[0077] Step 6, preparation of a sprayable anticorrosive coating

[0078] Mix and stir the solid phase of a sprayable anticorrosive coating and the liquid phase of a sprayable anticorrosive coating according to 1.5g / mL to form a fluid, and then high-pressure spray.

[0079] Example 3:

[0080] This example can construct and deconstruct S 2- According to the preparation method of the response anticorrosive coating, the following steps are implemented:

[0081] Step 1, preparation of copper-containing metal organic framework (HKUST-1)

[0082] Copper nitrate (Cu(NO3)2) was selected as the metal source and benzene-1,3,5-tricarboxylic acid (BTC) as the organic ligand to prepare HKUST-1 with specific pore structure and metal active sites. Cu(NO3)2 and BTC were dissolved in 50 mL of N,N-dimethylformamide at a molar ratio of 0.3:1, with a mass fraction of 3% for Cu(NO3)2. The mixed solution was transferred to a reaction kettle and reacted at 100°C for 24 h to allow the metal ions and organic ligands to self-assemble into HKUST-1 crystals. After the reaction was completed, the product was washed with dimethylformamide (DMF) and ethanol alternately for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was carried out at 70°C to remove solvent molecules in the pores, and finally vacuum drying was carried out to obtain HKUST-1, with a vacuum drying temperature of 70°C;

[0083] Step 2, preparation of ethylenediaminetetraacetic acid (EDTA) surface-modified HKUST-1 (E-HKUST-1)

[0084] 0.5 g of EDTA was weighed and dissolved in 50 mL of deionized water, and ultrasonic treatment was carried out for 20 min to make it completely dissolved to obtain an EDTA solution. 5 g of HKUST-1 crystals was weighed and added to the EDTA solution, and magnetic stirring was carried out at room temperature for 24 h to allow EDTA to fully interact with the surface of HKUST-1. After stirring, the mixed solution was transferred to a centrifuge tube and centrifuged at 5000 r / min to collect the precipitate. The precipitate was washed with deionized water for 5 times to remove unbound EDTA. The washed product was placed in a vacuum drying oven and dried at 75°C for 24 h to obtain EDTA surface-modified HKUST-1 (E-HKUST-1);

[0085] Step 3, preparation of poly(methyl methacrylate) (PMMA) grafted chitosan (CS) co-polymerized E-HKUST-1 core-shell microspheres (PCEH-1)

[0086] Take 4 g of chitosan, dissolve it in 200 mL of 1.5% mass fraction of acetic acid aqueous solution, stir at room temperature until completely dissolved, to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities, to obtain a clear chitosan solution for standby use. Mix the chitosan solution and methyl methacrylate (MMA) monomer in a three-necked flask according to a mass ratio of 1:1, with a total mass of 15 g, and add a water-ethanol mixed solution to the mixed system again, with an added amount of 100 mL of water and ethanol, and a volume ratio of 5:1, then according to the total mass percentage of the chitosan solution and the MMA monomer, add 5% methyl methacrylate (MMA), 8% polyvinylpyrrolidone (PVP), under the protection of an inert atmosphere, stir at 40℃ for 60 min, then, according to the total mass percentage of the chitosan solution and the MMA monomer, add 2% azobisisobutyronitrile (AIBN) and 0.6 g of E-HKUST-1, heat to 80℃, stir for 5 h, freeze-dry, to obtain poly methyl methacrylate (PMMA) grafted chitosan (CS) co-poly E-HKUST-1 core-shell microspheres (PCEH-1);

[0087] Step 4, preparation of a solid phase of a sprayable anticorrosive coating

[0088] Mix PCEH-1 and initiator dibenzoyl peroxide BPO, with a mass percentage of PCEH-1 of 99.8% and a mass percentage of BPO of 0.2%, to obtain a solid phase of a sprayable anticorrosive coating after mixing;

[0089] Step 5, preparation of a liquid phase of a sprayable anticorrosive coating

[0090] Mix methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine, and hydroquinone uniformly, to obtain a liquid phase of a sprayable anticorrosive coating; the mass percentages of the three are 98.5%, 2% and 0.5% respectively.

[0091] Step 6, preparation of a sprayable anticorrosive coating

[0092] Mix and stir the solid phase of a sprayable anticorrosive coating and the liquid phase of a sprayable anticorrosive coating according to 2 g / mL to form a fluid, and then high-pressure spray.

[0093] Example 4:

[0094] This example can construct and deconstruct the S of the antibacterial micro-interface 2- According to the method for preparing a response anticorrosive coating, the following steps are implemented:

[0095] Step 1, preparation of copper-containing metal organic framework (HKUST-1)

[0096] Copper nitrate (Cu(NO3)2) was chosen as the metal source and benzene-1,3,5-tricarboxylic acid (BTC) as the organic ligand to prepare HKUST-1 with specific pore structure and metal active sites. Cu(NO3)2 and BTC were dissolved in 50 mL of N,N-dimethylformamide (DMF) at a molar ratio of 0.4:1, with the mass fraction of Cu(NO3)2 being 4%. The mixed solution was transferred to a reaction kettle and reacted at 200°C for 24 h to allow the metal ions and organic ligands to self-assemble into HKUST-1 crystals. After the reaction, the product was washed with DMF and ethanol alternately for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was carried out at 70°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at 70°C.

[0097] Step 2, preparation of ethylenediaminetetraacetic acid (EDTA) surface-modified HKUST-1 (E-HKUST-1)

[0098] 1 g of EDTA was weighed and dissolved in 50 mL of deionized water, and ultrasonic treatment was carried out for 30 min to ensure complete dissolution, obtaining an EDTA solution. 10 g of HKUST-1 crystals was weighed and added to the EDTA solution, and magnetic stirring was carried out at room temperature for 24 h to allow EDTA to fully interact with the surface of HKUST-1. After stirring, the mixed solution was transferred to a centrifuge tube and centrifuged at 5000 r / min to collect the precipitate. The precipitate was washed with deionized water for 5 times to remove unbound EDTA. The washed product was placed in a vacuum drying oven and dried at 80°C for 24 h to obtain EDTA surface-modified HKUST-1 (E-HKUST-1).

[0099] Step 3, preparation of poly(methyl methacrylate) (PMMA) grafted chitosan (CS) co-polymerized E-HKUST-1 core-shell microspheres (PCEH-1)

[0100] 6g of chitosan was weighed and dissolved in 200mL of 2% mass fraction of acetic acid aqueous solution, stirred at room temperature until completely dissolved to obtain a chitosan solution. Filtered with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for standby use. CS and methyl methacrylate (MMA) monomer were mixed in a three-necked flask according to a mass ratio of 0.4:1, with a total mass of 10g, and a water-ethanol mixed solution was added again in the mixed system, with an amount of 100mL of water and ethanol, and a volume ratio of 5:1, then 3% methyl methacrylate (MMA) and 6% polyvinylpyrrolidone (PVP) were added according to the total mass percentage of chitosan solution and MMA monomer, and stirred at 40℃ for 60min under the protection of inert atmosphere, then 5% azobisisobutyronitrile (AIBN) and 1g of E-HKUST-1 were added again according to the total mass percentage of chitosan solution and MMA monomer, and stirred at 80℃ for 5h, and then freeze-dried to obtain poly(methyl methacrylate) (PMMA) grafted chitosan (CS) co-polymer E-HKUST-1 core-shell microspheres (PCEH-1);

[0101] Step 4, preparation of a solid phase of a sprayable anticorrosive coating

[0102] PCEH-1 and initiator dibenzoyl peroxide BPO were mixed, with a mass percentage of PCEH-1 of 99.9% and a mass percentage of BPO of 0.1%, and a solid phase of a sprayable anticorrosive coating was obtained after mixing;

[0103] Step 5, preparation of a liquid phase of a sprayable anticorrosive coating

[0104] Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone were mixed uniformly to obtain a liquid phase of a sprayable anticorrosive coating; the mass percentages of the three were 99.5%, 0.4% and 0.1% respectively.

[0105] Step 6, preparation of a sprayable anticorrosive coating

[0106] The solid phase of a sprayable anticorrosive coating and the liquid phase of a sprayable anticorrosive coating were mixed and stirred into a fluid according to 1g / mL, and then high-pressure spraying was performed.

[0107] Example 5:

[0108] This example can construct and deconstruct S 2- According to the method for preparing a response anticorrosive coating, the following steps were implemented:

[0109] Step 1, preparation of copper-containing metal organic framework (HKUST-1)

[0110] Cu(NO3)2was chosen as the metal source and benzene-1,3,5-tricarboxylic acid (BTC) as the organic ligand to prepare HKUST-1 with specific pore structure and metal active sites. Cu(NO3)2and BTC were dissolved in 40 mL of N,N-dimethylformamide (DMF) at a molar ratio of 0.35:1, and the mass fraction of Cu(NO3)2was 5%. The mixed solution was transferred to a reaction kettle and reacted at 180°C for 18 h to allow the metal ions and organic ligands to self-assemble into HKUST-1 crystals. After the reaction was completed, the product was washed with DMF and ethanol alternately for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was carried out at 60°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a temperature of 50°C.

[0111] Step 2, preparation of ethylenediaminetetraacetic acid (EDTA) surface modified HKUST-1 (E-HKUST-1)

[0112] 0.6 g of EDTA was weighed and dissolved in 20 mL of deionized water, and ultrasonic treatment was carried out for 30 min to ensure complete dissolution, obtaining an EDTA solution. 10 g of HKUST-1 crystals was weighed and added to the EDTA solution, and magnetic stirring was carried out at room temperature for 24 h to allow EDTA to fully interact with the surface of HKUST-1. After stirring, the mixed solution was transferred to a centrifuge tube and centrifuged at 5000 r / min to collect the precipitate. The precipitate was washed with deionized water for 5 times to remove unbound EDTA. The washed product was placed in a vacuum drying oven and dried at 65°C for 18 h to obtain EDTA surface modified HKUST-1 (E-HKUST-1);

[0113] Step 3, preparation of poly(methyl methacrylate) (PMMA) grafted chitosan (CS) co-polymerized E-HKUST-1 core-shell microspheres (PCEH-1)

[0114] Take 4 g of chitosan, dissolve it in 200 mL of 2% mass fraction of acetic acid aqueous solution, stir at room temperature until completely dissolved, to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities, to obtain a clear chitosan solution for standby use. Mix the chitosan solution and methyl methacrylate (MMA) monomer in a three-necked flask according to the mass ratio of 0.6:1, with a total mass of 15 g, and add a water-ethanol mixed solution to the mixed system again, with the addition amount of water and ethanol being 100 mL, and the volume ratio being 2.5:1, then according to the total mass percentage of chitosan solution and MMA monomer, add 3% methyl methacrylate (MMA), 6% polyvinylpyrrolidone (PVP), under the protection of inert atmosphere, stir at 30℃ for 60 min, then, according to the total mass percentage of chitosan solution and MMA monomer, add 1% azobisisobutyronitrile (AIBN) and 0.5 g of E-HKUST-1, heat to 70℃, stir for 5 h, freeze-dry, to obtain poly methyl methacrylate (PMMA) grafted chitosan (CS) co-poly E-HKUST-1 core-shell microspheres (PCEH-1);

[0115] Step 4, preparation of a solid phase of a sprayable anticorrosive coating

[0116] Mix PCEH-1 and initiator dibenzoyl peroxide BPO, with the mass percentage of PCEH-1 being 99.9% and the mass percentage of BPO being 0.1%, to obtain a solid phase of a sprayable anticorrosive coating after mixing;

[0117] Step 5, preparation of a liquid phase of a sprayable anticorrosive coating

[0118] Mix methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone uniformly, to obtain a liquid phase of a sprayable anticorrosive coating; the mass percentages of the three are 97.5%, 2% and 0.5% respectively.

[0119] Step 6, preparation of a sprayable anticorrosive coating

[0120] Mix and stir the solid phase of a sprayable anticorrosive coating and the liquid phase of a sprayable anticorrosive coating according to 2 g / mL to form a fluid, and then high-pressure spray.

[0121] Example 6:

[0122] This example can construct and deconstruct the S of the antibacterial micro-interface 2- In response to the preparation method of the anticorrosive coating, the following steps are implemented:

[0123] Step 1, preparation of copper-containing metal organic framework (HKUST-1)

[0124] HKUST-1 with specific pore structure and metal active sites was prepared by selecting copper nitrate (Cu(NO3)2) as metal source and benzene-1,3,5-tricarboxylic acid (BTC) as organic ligand. Cu(NO3)2 and BTC were dissolved in 50 mL of N,N-dimethylformamide (DMF) at a molar ratio of 0.5:1, and the mass fraction of Cu(NO3)2 was 4%. The mixed solution was transferred to a reaction kettle and reacted at 200°C for 18 h to allow metal ions and organic ligands to self-assemble into HKUST-1 crystals. After the reaction was completed, the product was washed with DMF and ethanol alternately 4 times to remove unreacted raw materials and impurities. Then, an activation treatment was carried out at 70°C to remove solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at 70°C;

[0125] Step 2, preparation of ethylenediaminetetraacetic acid (EDTA) surface modified HKUST-1 (E-HKUST-1)

[0126] 2.5 g of EDTA was weighed and dissolved in 50 mL of deionized water, and ultrasonic treatment was carried out for 30 min to make it completely dissolved to obtain an EDTA solution. 10 g of HKUST-1 crystals was weighed and added to the EDTA solution, and magnetic stirring was carried out at room temperature for 24 h to allow EDTA to fully interact with the surface of HKUST-1. After stirring, the mixed solution was transferred to a centrifuge tube and centrifuged at 4000 r / min to collect the precipitate. The precipitate was washed with deionized water 5 times to remove unbound EDTA by centrifugation. The washed product was placed in a vacuum drying oven and dried at 80°C for 24 h to obtain EDTA surface modified HKUST-1 (E-HKUST-1);

[0127] Step 3, preparation of poly(methyl methacrylate) (PMMA) grafted chitosan (CS) co-polymerized E-HKUST-1 core-shell microspheres (PCEH-1)

[0128] 6g of chitosan was weighed and dissolved in 200mL of 2% mass fraction of acetic acid aqueous solution, stirred at room temperature until completely dissolved, to obtain a chitosan solution. Filtered with a filter membrane to remove insoluble impurities, to obtain a clear chitosan solution for standby use. CS and methyl methacrylate (MMA) monomers were mixed in a three-necked flask at a mass ratio of 0.4:1, with a total mass of 10g, and a water-ethanol mixed solution was further added to the mixed system, with an amount of 100mL, and a volume ratio of 5:1, then 3% methyl methacrylate (MMA) and 6% polyvinylpyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 40°C for 50min under the protection of an inert atmosphere, then 5% azobisisobutyronitrile (AIBN) and 1g of E-HKUST-1 were further added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 80°C for 5h, and then freeze-dried to obtain poly methyl methacrylate (PMMA) grafted chitosan (CS) co-polymer E-HKUST-1 core-shell microspheres (PCEH-1);

[0129] Step 4, preparation of a solid phase of a sprayable anticorrosive coating

[0130] PCEH-1 and initiator dibenzoyl peroxide BPO were mixed, with a mass percentage of PCEH-1 of 99.8% and a mass percentage of BPO of 0.2%, to obtain a solid phase of a sprayable anticorrosive coating after mixing;

[0131] Step 5, preparation of a liquid phase of a sprayable anticorrosive coating

[0132] Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone were mixed uniformly to obtain a liquid phase of a sprayable anticorrosive coating; the mass percentages of the three were 99.5%, 0.4% and 0.1% respectively.

[0133] Step 6, preparation of a sprayable anticorrosive coating

[0134] After the solid phase of a sprayable anticorrosive coating and the liquid phase of a sprayable anticorrosive coating were mixed and stirred into a fluid at a ratio of 1.5g / mL, high-pressure spraying was performed.

[0135] It was verified that after the anticorrosive coating prepared in Examples 1-6 of the present application was sprayed on the surface of a metal and co-cultured with sulfate-reducing bacteria for 30 days, no corrosion occurred on the surface of the metal, and no antibacterial ions were present in the culture solution after detection by a flame atomic spectrophotometer. As shown in Table 1, at 10 days, 20 days and 30 days, the sample was taken out of the culture solution, and a bacterial suspension was obtained by ultrasonic treatment, and no obvious bacterial colonies were produced after agar plate coating, indicating excellent antibacterial effect of the coating. The above results show that the S Figure 1 ​2- The responsive underground anti-corrosion coating can precisely respond to the construction of antibacterial micro-interfaces, achieving excellent anti-corrosion effects.

Claims

1. Recyclable construction-deconstruction of antibacterial micro-interfaces S 2- The method for preparing a responsive anti-corrosion coating is characterized in that, The specific steps are as follows: Step 1: Prepare copper-containing metal-organic framework HKUST-1; Step 2: Surface modification of HKUST-1 obtained in Step 1 with ethylenediaminetetraacetic acid to obtain E-HKUST-1; Step 3: Using E-HKUST-1 obtained in Step 2 as the polymerization site, core-shell polymethyl methacrylate-grafted chitosan copolymer E-HKUST-1 core-shell microspheres, namely PCEH-1, are prepared by solution polymerization. Step 4: Prepare a solid phase for spraying an anti-corrosion coating; Step 5: Prepare a liquid phase suitable for spraying anti-corrosion coatings; Step 6: Mix the solid and liquid phases prepared in steps 4 and 5 at a concentration of 1~2 g / mL and stir to form a fluid. Then, spray the mixture under high pressure to obtain the anti-corrosion coating. Step 3 specifically involves: Chitosan solution was mixed with methyl methacrylate, and then water-ethanol mixture was added. Methylenebisacrylamide and polyvinylpyrrolidone were added to the reaction system. Under an inert atmosphere, the mixture was stirred at 30-40°C for 30-60 min. Then azobisisobutyronitrile and E-HKUST-1 obtained in step 2 were added. The temperature was raised to 70-80°C and stirred for 3-5 h. After freeze-drying, core-shell microspheres PCEH-1 were obtained. Step 4 is as follows: The PCEH-1 obtained in step 3 and the initiator benzoyl peroxide (BPO) are mixed to obtain a sprayable anti-corrosion coating solid phase, wherein the mass percentage of PCEH-1 is 99.8%~99.9% and the mass percentage of BPO is 0.1%~0.2%. Step 5 specifically involves: The liquid phase of the sprayable anti-corrosion coating is prepared by uniformly mixing methyl methacrylate monomer, N,N-dimethyl-p-toluidine, and hydroquinone; wherein the mass percentage of methyl methacrylate monomer is 96.5-99.5%, the mass percentage of N,N-dimethyl-p-toluidine is 0.4-3%, and the mass percentage of hydroquinone is 0.1-0.5%.

2. The S-type recyclable construction-deconstruction antibacterial micro-interface according to claim 1 2- The method for preparing a responsive anti-corrosion coating is characterized in that, Step 1 is as follows: Cu(NO3)2 and trimesic acid were dissolved in N,N-dimethylformamide at a molar ratio of 0.1-0.5:1, wherein the mass fraction of Cu(NO3)2 was 1-5%. The mixed solution was reacted at 100-200℃ for 12-24 h to allow the metal ions and organic ligands to self-assemble into HKUST-1 crystals. After the reaction, the product was washed with dimethylformamide and ethanol alternately 3-5 times to remove unreacted raw materials and impurities. Then, it was activated at 50-70℃ to remove solvent molecules in the pores. Finally, it was vacuum dried at 50-70℃ to obtain HKUST-1.

3. The S-type recyclable construction-deconstruction antibacterial micro-interface according to claim 1 2- The method for preparing a responsive anti-corrosion coating is characterized in that, Step 2 is as follows: The HKUST-1 obtained in step 1 was added to an ethylenediaminetetraacetic acid (EDTA) solution and stirred at room temperature for 12-24 hours to allow the EDTA to fully interact with the surface of HKUST-1. The reaction solution was then centrifuged, the precipitate was collected and washed with deionized water, and the washed product was dried in a vacuum drying oven at 60-80°C for 12-24 hours to obtain E-HKUST-1.

4. The S-type recyclable construction-deconstruction antibacterial micro-interface according to claim 3 2- The method for preparing a responsive anti-corrosion coating is characterized in that, The mass fraction of the ethylenediaminetetraacetic acid solution is 1-5%; the mass ratio of HKUST-1 to ethylenediaminetetraacetic acid is 2-25:1; and the centrifugation rate is 3000-5000 r / min.

5. The S-type recyclable construction-deconstruction antibacterial micro-interface according to claim 1 2- The method for preparing a responsive anti-corrosion coating is characterized in that, The specific preparation method of chitosan solution is as follows: dissolve chitosan in an aqueous solution of acetic acid with a mass fraction of 1~2%, stir at room temperature until completely dissolved, wherein the mass fraction of chitosan is 1~6%; filter with a filter membrane to remove insoluble impurities to obtain chitosan solution.

6. The S-type recyclable construction-deconstruction antibacterial micro-interface according to claim 1 2- The method for preparing a responsive anti-corrosion coating is characterized in that, The mass ratio of chitosan solution to methyl methacrylate is 0.1 to 1:1; the volume ratio of water to ethanol in the water-ethanol mixed solution is 2 to 5:

1.

7. The S-type recyclable construction-deconstruction antibacterial micro-interface according to claim 1 2- The method for preparing a responsive anti-corrosion coating is characterized in that, The mass percentages of methylene bisacrylamide, polyvinylpyrrolidone, azobisisobutyronitrile, and E-HKUST-1 added in step 3 are 1-5%, 2-8%, 1-5%, and 1-10% of the total mass of chitosan solution and methyl methacrylate, respectively.

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