Preparation method of S < 2->-response anticorrosive coating capable of cyclically constructing-deconstructing antibacterial micro-interface

Abstract

The invention discloses a preparation method of an S < 2->-response anticorrosive coating capable of circularly constructing and deconstructing an antibacterial micro-interface. The preparation method comprises the following steps: preparing a copper-containing metal organic framework HKUST-1; the preparation method comprises the following steps: carrying out surface modification on HKUST-1 by using ethylenediamine tetraacetic acid to obtain E-HKUST-1; the preparation method comprises the following steps: by taking E-HKUST-1 as a polymerization site, preparing core-shell polymethyl methacrylate grafted chitosan copolymerized E-HKUST-1 core-shell microspheres, namely PCEH-1, through a solution polymerization method; preparing a solid phase and a liquid phase which can be sprayed with an anti-corrosion coating; the solid phase and the liquid phase are mixed and stirred into fluid according to the concentration of 1-2 g / mL, then high-pressure spraying is conducted, and the anti-corrosion coating is obtained. The coating prepared by the method disclosed by the invention has the characteristics that an antibacterial micro-interface can be circularly constructed and deconstructed, and the anti-corrosion effect is long-term and stable.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal anti-corrosion coating preparation methods, and particularly relates to a preparation method of an S 2- -responsive anti-corrosion coating capable of cyclically constructing and deconstructing antibacterial micro-interfaces. Background Art

[0002] Bacteria can cause pitting corrosion, crevice corrosion, etc. on the alloy surface by means of metabolites and forming biofilms. In the field of power engineering, sulfate-reducing bacteria corrosion is one of the main factors leading to the failure of underground cable signal transmission. The cable shielding layer and armor of the power transmission system are mostly made of alloy materials. After the alloy shielding layer is corroded, the electromagnetic shielding ability decreases, affecting signal transmission, and the metal mechanical strength decreases, making the cable more likely to be damaged due to external forces during laying and use. When the insulating layer is eroded by sulfate-reducing bacteria, the insulation performance deteriorates rapidly, leading to electric leakage and short circuit, resulting in the interruption of power transmission and affecting the power supply stability. In addition, the continuous erosion of sulfate-reducing bacteria accelerates the aging of the cable, shortens the service life, increases the maintenance cost and potential safety hazards, causing huge losses to the power system.

[0003] A new generation of alloy anti-corrosion materials represented by sulfur ion (S 2- )-responsive ion-releasing anti-corrosion coatings have the ability to actively recognize sulfate-reducing bacteria and their metabolites. By sensing specific chemical reactions or physical changes and dynamically regulating the ion release concentration according to the actual situation of the complex and changeable environment, they can significantly inhibit the growth of sulfate-reducing bacteria and effectively prevent bacterial corrosion. Compared with traditional anti-corrosion coatings, S 2- -responsive anti-corrosion coatings show more excellent performance. However, the existing S 2- -responsive anti-corrosion coatings have continuous leakage of antibacterial substances after response, which will not only have a negative impact on the long-term stability of the coating anti-corrosion performance, but also may pose potential ecological risks to the surrounding soil and water environment.

[0004] The Chinese patent "An Anticorrosive Filler with Intelligent Response, Its Preparation Method and Application" (Application No.: 202310316576.8, Publication Date: January 23, 2024, Publication No.: CN116285463B) discloses an anticorrosive filler with intelligent response, its preparation method and application. The Chinese patent "An Intelligent Response Self-Healing Anticorrosive Coating Material and Preparation Method" (Application No.: 201910365017.X, Publication Date: August 2, 2019, Publication No.: CN110079140A) discloses an intelligent response self-healing anticorrosive coating material and preparation method. The intelligent response anticorrosive materials disclosed in these two patents will accelerate the release of corrosion inhibitors and delay corrosion when the environmental pH value is acidic. However, once the environmental change is responded to, the corrosion inhibitor will continuously leak, which will have a negative impact on the long-term anticorrosive performance of the coating and pose potential ecological risks to the surrounding soil and water environment.

[0005] Obviously, it is of crucial significance to develop other new environmentally responsive anticorrosive coatings, providing new ideas and technical support for the development of more green and sustainable alloy anticorrosive materials. Summary of the Invention

[0006] The object of the present invention is to provide a preparation method of an S 2- responsive anticorrosive coating capable of cyclic construction-destruction of antibacterial microinterfaces. The coating prepared by this method has the characteristics of cyclic construction-destruction of antibacterial microinterfaces and long-term stable anticorrosive effect.

[0007] The technical solution adopted by the present invention is a preparation method of an S 2- responsive anticorrosive coating capable of cyclic construction-destruction of antibacterial microinterfaces, which is specifically implemented according to the following steps: Step 1: Prepare copper-containing metal-organic framework HKUST-1; Step 2: Surface-modify the HKUST-1 obtained in Step 1 with ethylenediaminetetraacetic acid to obtain E-HKUST-1; Step 3: Using the E-HKUST-1 obtained in Step 2 as a polymerization site, prepare core-shell poly(methyl methacrylate) grafted chitosan copolymer E-HKUST-1 core-shell microspheres, namely PCEH-1, by solution polymerization; Step 4: Prepare a solid phase for the sprayable anticorrosive coating; Step 5: Prepare a liquid phase for the sprayable anticorrosive coating; Step 6: Mix the solid phase and liquid phase prepared in Steps 4 and 5 at a concentration of 1-2 g / mL, stir into a fluid, and then spray it under high pressure to obtain the anticorrosive coating.

[0008] The characteristics of the present invention also lie in: Step 1 is specifically as follows: Mix Cu(NO 3) 2 and trimesic acid in a molar ratio of 0.1~0.5:1 are dissolved in N,N-dimethylformamide, where Cu(NO 3 ) 2 The mass fraction of HKUST-1 is 1-5%; the mixed solution is reacted at 100-200°C for 12-24h to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals; after the reaction, the product is washed alternately with dimethylformamide and ethanol for 3-5 times to remove unreacted raw materials and impurities, and then activated at 50-70°C to remove the solvent molecules in the pores, and finally vacuum dried at 50-70°C to obtain HKUST-1.

[0009] Step 2 is as follows: The HKUST-1 obtained in step 1 is added to an ethylenediaminetetraacetic acid solution and stirred at room temperature for 12 to 24 hours to allow the ethylenediaminetetraacetic acid to fully interact with the surface of HKUST-1; the reaction solution is then centrifuged, the precipitate is collected and washed with deionized water, and the washed product is dried in a vacuum drying oven at 60 to 80° C. for 12 to 24 hours to obtain E-HKUST-1.

[0010] The mass fraction of EDTA solution is 1-5%; the mass ratio of HKUST-1 to EDTA is 2-25:1; and the centrifugal speed is 3000-5000 r / min.

[0011] Step 3 is as follows: The chitosan solution was mixed with methyl methacrylate, and then a water-ethanol mixed solution was added. Then, methylenebisacrylamide and polyvinyl pyrrolidone were added to the reaction system. Under the protection of an inert atmosphere, the mixture was stirred at 30-40° C. for 30-60 min. Then, azobisisobutyronitrile and the E-HKUST-1 obtained in step 2 were added. The mixture was heated to 70-80° C., stirred for 3-5 h, and then freeze-dried to obtain core-shell microspheres PCEH-1.

[0012] The specific preparation method of the chitosan solution is: dissolving chitosan in an acetic acid aqueous solution with a mass fraction of 1-2%, stirring at room temperature until completely dissolved, wherein the mass fraction of chitosan is 1-6%; filtering with a filter membrane to remove insoluble impurities to obtain a chitosan solution.

[0013] The mass ratio of chitosan solution to methyl methacrylate is 0.1-1:1; the volume ratio of water to ethanol in the water-ethanol mixed solution is 2-5:1.

[0014] The masses of methylenebisacrylamide, polyvinyl pyrrolidone, azobisisobutyronitrile and E-HKUST-1 added in step 3 are 1-5%, 2-8%, 1-5% and 1-10% of the total mass of the chitosan solution and methyl methacrylate, respectively.

[0015] Step 4 is as follows: The PCEH-1 obtained in step 3 and the initiator dibenzoyl peroxide BPO are mixed to obtain a sprayable anti-corrosion coating solid phase, wherein the mass percentage of PCEH-1 is 99.8% to 99.9%, and the mass percentage of BPO is 0.1 to 0.2%.

[0016] Step 5 is as follows: Evenly mix methyl methacrylate monomer, N,N-dimethyl-p-toluidine and hydroquinone to obtain a sprayable anti-corrosion 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%.

[0017] The beneficial effects of the present invention are: (1) The core-shell microspheres in the anti-corrosion coating of the present invention are formed by self-polymerization, and the core material E-HKUST-1 reacts with the metabolite S of underground corrosion bacteria (sulfate-reducing bacteria) to form a 2- With highly accurate response characteristics. 2- Destruction of organic ligand trimesic acid and Cu 2+ The inter-coordinate bond initiates dissociation and promotes Cu 2+ The chitosan molecules in the outer layer, which are rich in amino and hydroxyl groups, continue to diffuse outward and interact with Cu through electrostatic and coordination effects. 2+ Recombined with each other, the Cu 2+ Fixed on the surface of the microspheres, it appears as an antibacterial microinterface in the coating-soil contact area on a macroscopic scale. The constructed antibacterial microinterface can significantly inhibit the growth of sulfate-reducing bacteria on the coating surface, effectively preventing bacterial corrosion; in addition, the antibacterial microinterface effectively avoids the coating S 2- The continuous release of antibacterial substances after the response ensures the long-term anti-corrosion performance of the coating while reducing potential risks to the ecological environment.

[0018] (2) The method of the present invention relies on the difference in the coordination ability of different ligands to antibacterial ions and uses the ligand competition mechanism to achieve the dynamic cycle construction and deconstruction of the responsive antibacterial micro-interface in the coating system, specifically: The death of sulfate-reducing bacteria leads to S 2- After the signal disappears, the dissociation process of E-HKUST-1 is terminated, and the antibacterial microinterface is constructed. Subsequently, according to the coordination competition principle, the surface modification of E-HKUST-1 with EDTA, which has strong coordination competition ability, will make Cu 2+ Dissociate from chitosan molecules and re-chelate to E-HKUST-1, resulting in the deconstruction of the antibacterial microinterface. 2-The signal reappears, the decoupling process of E-HKUST-1 is reactivated, and the antibacterial microinterface is formed again.

[0019] This dynamic cycle construction process is not a simple periodic change, but a self-response call and re-storage of antibacterial and antiseptic substances based on the material's microstructure and chemical composition to external signal stimulation, ensuring that the coating maintains the high efficiency and permanent effectiveness of its anti-corrosion function.

[0020] (3) S prepared by the method of the present invention 2- The underground anti-corrosion coating with responsive and recyclable construction-deconstruction antibacterial micro-interface has a long-term stable and green anti-corrosion effect. In the field of metal anti-corrosion, this coating technology is expected to break through the limitations of traditional anti-corrosion methods and provide a new, efficient and green solution for the protection of underground metal facilities, with broad application prospects and significant economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The figure is a colony detection result diagram after coating the coating prepared by the method of the present invention on an agar plate. DETAILED DESCRIPTION

[0022] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0023] The present invention can cyclically construct and deconstruct the S of antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare a MOF (HKUST-1) with a specific pore structure and metal active sites. 3 ) 2 and BTC were dissolved in N,N-dimethylformamide at a molar ratio of 0.1-0.5:1, where Cu(NO 3 ) 2 The mass fraction of is 1~5%; the mixed solution is transferred to a reactor and reacted at 100~200℃ for 12~24h to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product is washed alternately with dimethylformamide (DMF) and ethanol for 3~5 times to remove unreacted raw materials and impurities. Then, an activation treatment is performed at 50~70℃ to remove the solvent molecules in the pores, and finally, HKUST-1 is obtained by vacuum drying at 50~70℃; Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Dissolve EDTA in deionized water and perform ultrasonic treatment for 15 to 30 minutes to completely dissolve it to obtain an EDTA solution in which the mass fraction of EDTA is 1 to 5%. Weigh the HKUST-1 crystals obtained in step 1, the mass ratio of HKUST-1 crystals to EDTA is 2-25:1, add them to the EDTA solution, and stir magnetically at room temperature for 12 to 24 hours to allow EDTA to fully interact with the surface of HKUST-1. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 3000 to 5000 r / min, and collect the precipitate. Wash the precipitate with deionized water 3 to 5 times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 60 to 80°C for 12 to 24 hours to obtain EDTA surface-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Dissolve chitosan in 1-2% acetic acid aqueous solution, stir at room temperature until completely dissolved, and obtain a chitosan solution, wherein the mass fraction of chitosan is 1-6%. Filter with a filter membrane to remove insoluble impurities, and obtain a clear chitosan solution for use. Chitosan solution (CS) and methyl methacrylate (MMA) monomer are mixed in a three-necked flask at a mass ratio of 0.1-1:1, and a water-ethanol mixed solution is added to the mixed system again, and the volume ratio of water to ethanol in the mixed solution is 2-5:1, and then 1-5% methylenebisacrylamide (MBA) and 2-8% polyvinylpyrrolidone (PVP) are added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 30-40°C for 30-60min under the protection of an inert atmosphere. Subsequently, 1-5% azobisisobutyronitrile (AIBN) and 1-10% E-HKUST-1 are added again according to the total mass percentage of the chitosan solution and the MMA monomer, and the temperature is raised to 70-80°C, stirred for 3-5h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase Mix PCEH-1 and initiator dibenzoyl peroxide BPO, wherein the mass percentage of PCEH-1 is 99.8% to 99.9% and the mass percentage of BPO is 0.1% to 0.2%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, Preparation of Sprayable Anticorrosive Coating Liquid Phase Evenly mix methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone to obtain a sprayable anti-corrosion 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%.

[0024] Step 6: Sprayable anti-corrosion coating preparation After the solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at a concentration of 1-2 g / mL, high-pressure spraying can be performed.

[0025] The present invention can cyclically construct and deconstruct the S of antibacterial micro-interface 2- The preparation method of the responsive anti-corrosion coating is firstly prepared by self-coordination and surface modification technology to prepare a copper-containing metal organic framework (E-HKUST-1); secondly, using E-HKUST-1 as the polymerization site, a solution polymerization method is used to prepare core-shell polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymer E-HKUST-1 core-shell microspheres (PCEH-1); PCEH-1 and initiator BPO are uniformly mixed in a certain mass ratio to obtain a sprayable anti-corrosion coating solid phase; MMA, N,N-dimethyl-p-toluidine, and hydroquinone are uniformly mixed in a certain mass ratio to obtain a sprayable anti-corrosion coating liquid phase; the solid phase and the liquid phase are mixed and stirred and sprayed under high pressure.

[0026] Embodiment 1: This embodiment can cyclically construct and deconstruct the S of the antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare HKUST-1 with a specific pore structure and metal active sites. 3 ) 2 and BTC were dissolved in 20 mL of N,N-dimethylformamide at a molar ratio of 0.1:1, where Cu(NO 3 ) 2 The mass fraction of is 1%. The mixed solution was transferred to a reactor and reacted at 100°C for 12 hours to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product was washed alternately with dimethylformamide (DMF) and ethanol for 3 times to remove unreacted raw materials and impurities. Then, an activation treatment was performed at 50°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a vacuum drying temperature of 50°C. Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Weigh 0.2 g of EDTA, dissolve it in 20 mL of deionized water, and ultrasonically treat it for 15 minutes to completely dissolve it to obtain an EDTA solution. Weigh 5 g of HKUST-1 crystals, add them to the EDTA solution, and magnetically stir at room temperature for 12 hours to allow EDTA to fully interact with the HKUST-1 surface. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 3000 r / min, and collect the precipitate. Wash the precipitate with deionized water three times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 60°C for 12 hours to obtain EDTA-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Weigh 2 g of chitosan, dissolve it in 100 mL of 1% by mass acetic acid aqueous solution, and stir at room temperature until it is completely dissolved to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for use. Chitosan solution and methyl methacrylate (MMA) monomer were mixed in a three-necked flask at a mass ratio of 0.1:1, with a total mass of 10 g, and a water-ethanol mixed solution was added to the mixed system again, with the addition amount of water and ethanol being 100 mL, and the volume ratio being 2:1, and then 1% methyl methacrylate (MMA) and 2% polyvinyl pyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 30°C for 30 min under the protection of an inert atmosphere, and then 1% azobisisobutyronitrile (AIBN) and 0.1 g of E-HKUST-1 were added again according to the total mass percentage of the chitosan solution and the MMA monomer, the temperature was raised to 70°C, stirred for 3 h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase Mix PCEH-1 and initiator dibenzoyl peroxide BPO, wherein the mass percentage of PCEH-1 is 99.9% and the mass percentage of BPO is 0.1%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, preparation of sprayable anticorrosive coating liquid phase Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone are uniformly mixed to obtain a sprayable anti-corrosion coating liquid phase; the mass percentages of the three are 96.5, 3% and 0.5% respectively.

[0027] Step 6: Sprayable anti-corrosion coating preparation The solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at 1g / mL, and then high-pressure spraying is performed.

[0028] Embodiment 2: This embodiment can cyclically construct and deconstruct the S of the antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare HKUST-1 with a specific pore structure and metal active sites. 3 ) 2 and BTC were dissolved in 20 mL of N,N-dimethylformamide at a molar ratio of 0.2:1, where Cu(NO 3 ) 2 The mass fraction of is 2%. The mixed solution was transferred to a reactor and reacted at 200°C for 12 hours to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product was washed alternately with dimethylformamide (DMF) and ethanol for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was performed at 65°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a vacuum drying temperature of 60°C. Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Weigh 0.5 g of EDTA, dissolve it in 50 mL of deionized water, and ultrasonically treat for 30 minutes to completely dissolve it to obtain an EDTA solution. Weigh 7.5 g of HKUST-1 crystals, add them to the EDTA solution, and magnetically stir at room temperature for 24 hours to allow EDTA to fully interact with the HKUST-1 surface. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 5000 r / min, and collect the precipitate. Wash the precipitate with deionized water 5 times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 80°C for 24 hours to obtain EDTA surface-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Weigh 3 g of chitosan, dissolve it in 100 mL of 1% by mass acetic acid aqueous solution, and stir at room temperature until it is completely dissolved to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for use. Chitosan solution and methyl methacrylate (MMA) monomer were mixed in a three-necked flask at a mass ratio of 0.5:1, with a total mass of 10 g, and a water-ethanol mixed solution was added to the mixed system again, with the addition amount of water and ethanol being 100 mL and the volume ratio being 5:1, and then 2% methyl methacrylate (MMA) and 4% polyvinyl pyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 40°C for 40 min under the protection of an inert atmosphere, and then 5% azobisisobutyronitrile (AIBN) and 0.4 g of E-HKUST-1 were added again according to the total mass percentage of the chitosan solution and the MMA monomer, the temperature was raised to 75°C, stirred for 5 h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase 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%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, preparation of sprayable anticorrosive coating liquid phase Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone are uniformly mixed to obtain a sprayable anti-corrosion coating liquid phase; the mass percentages of the three are 97.5%, 2% and 0.5% respectively.

[0029] Step 6: Sprayable anti-corrosion coating preparation The solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at a concentration of 1.5 g / mL, and then high-pressure spraying is performed.

[0030] Embodiment 3: This embodiment can cyclically construct and deconstruct the S of the antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare HKUST-1 with a specific pore structure and metal active sites. 3 ) 2and BTC were dissolved in 50 mL of N,N-dimethylformamide at a molar ratio of 0.3:1, where Cu(NO 3 ) 2 The mass fraction is 3%. The mixed solution was transferred to a reactor and reacted at 100°C for 24 hours to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product was washed alternately with dimethylformamide (DMF) and ethanol for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was performed at 70°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a vacuum drying temperature of 70°C. Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Weigh 0.5 g of EDTA, dissolve it in 50 mL of deionized water, and ultrasonically treat it for 20 minutes to completely dissolve it to obtain an EDTA solution. Weigh 5 g of HKUST-1 crystals, add them to the EDTA solution, and magnetically stir at room temperature for 24 hours to allow EDTA to fully interact with the HKUST-1 surface. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 5000 r / min, and collect the precipitate. Wash the precipitate with deionized water 5 times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 75°C for 24 hours to obtain EDTA surface-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Weigh 4 g of chitosan, dissolve it in 200 mL of 1.5% by mass acetic acid aqueous solution, and stir at room temperature until it is completely dissolved to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for use. Chitosan solution and methyl methacrylate (MMA) monomer were mixed in a three-necked flask at a mass ratio of 1:1, with a total mass of 15 g, and a water-ethanol mixed solution was added to the mixed system again, with the addition amount of water and ethanol being 100 mL and the volume ratio being 5:1, and then 5% methyl methacrylate (MMA) and 8% polyvinyl pyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 40°C for 60 min under the protection of an inert atmosphere, and then 2% azobisisobutyronitrile (AIBN) and 0.6 g of E-HKUST-1 were added again according to the total mass percentage of the chitosan solution and the MMA monomer, the temperature was raised to 80°C, stirred for 5 h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase 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%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, Preparation of Sprayable Anticorrosive Coating Liquid Phase Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone are uniformly mixed to obtain a sprayable anti-corrosion coating liquid phase; the mass percentages of the three are 98.5%, 2% and 0.5% respectively.

[0031] Step 6: Sprayable anti-corrosion coating preparation The solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at 2g / mL, and then high-pressure spraying is performed.

[0032] Embodiment 4: This embodiment can cyclically construct and deconstruct the S of the antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare HKUST-1 with a specific pore structure and metal active sites. 3 ) 2 and BTC were dissolved in 50 mL of N,N-dimethylformamide at a molar ratio of 0.4:1, where Cu(NO 3 ) 2 The mass fraction is 4%. The mixed solution was transferred to a reactor and reacted at 200°C for 24 hours to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product was washed alternately with dimethylformamide (DMF) and ethanol for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was performed at 70°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a vacuum drying temperature of 70°C. Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Weigh 1g of EDTA, dissolve it in 50mL of deionized water, and ultrasonically treat for 30min to completely dissolve it to obtain EDTA solution. Weigh 10g of HKUST-1 crystals, add them to the EDTA solution, and magnetically stir at room temperature for 24h to allow EDTA to fully interact with the HKUST-1 surface. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 5000r / min, and collect the precipitate. Wash the precipitate with deionized water 5 times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 80℃ for 24h to obtain EDTA surface-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Weigh 6 g of chitosan, dissolve it in 200 mL of 2% by mass acetic acid aqueous solution, and stir at room temperature until it is completely dissolved to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for 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 10 g, and a water-ethanol mixed solution was added to the mixed system again, with the addition amount of water and ethanol being 100 mL and the volume ratio being 5:1, and then 3% methyl methacrylate (MMA) and 6% polyvinyl pyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 40°C for 60 min under the protection of an inert atmosphere, and then 5% azobisisobutyronitrile (AIBN) and 1 g of E-HKUST-1 were added again according to the total mass percentage of the chitosan solution and the MMA monomer, the temperature was raised to 80°C, stirred for 5 h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase Mix PCEH-1 and initiator dibenzoyl peroxide BPO, wherein the mass percentage of PCEH-1 is 99.9% and the mass percentage of BPO is 0.1%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, Preparation of Sprayable Anticorrosive Coating Liquid Phase Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone are uniformly mixed to obtain a sprayable anti-corrosion coating liquid phase; the mass percentages of the three are 99.5%, 0.4% and 0.1% respectively.

[0033] Step 6: Sprayable anti-corrosion coating preparation The solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at 1g / mL, and then high-pressure spraying is performed.

[0034] Embodiment 5: This embodiment can cyclically construct and deconstruct the S of the antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare HKUST-1 with a specific pore structure and metal active sites. 3 ) 2 and BTC were dissolved in 40 mL of N,N-dimethylformamide at a molar ratio of 0.35:1, where Cu(NO 3 ) 2 The mass fraction of is 5%. The mixed solution was transferred to a reactor and reacted at 180°C for 18 hours to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product was washed alternately with dimethylformamide (DMF) and ethanol for 5 times to remove unreacted raw materials and impurities. Then, an activation treatment was performed at 60°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a vacuum drying temperature of 50°C. Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Weigh 0.6 g of EDTA, dissolve it in 20 mL of deionized water, and ultrasonically treat it for 30 minutes to completely dissolve it to obtain an EDTA solution. Weigh 10 g of HKUST-1 crystals, add them to the EDTA solution, and magnetically stir at room temperature for 24 hours to allow EDTA to fully interact with the HKUST-1 surface. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 5000 r / min, and collect the precipitate. Wash the precipitate with deionized water 5 times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 65°C for 18 hours to obtain EDTA surface-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Weigh 4 g of chitosan, dissolve it in 200 mL of 2% by mass acetic acid aqueous solution, and stir at room temperature until it is completely dissolved to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for use. Chitosan solution and methyl methacrylate (MMA) monomer were mixed in a three-necked flask at a mass ratio of 0.6:1, with a total mass of 15 g, and a water-ethanol mixed solution was added to the mixed system again, with the addition amount of water and ethanol being 100 mL and the volume ratio being 2.5:1, and then 3% methyl methacrylate (MMA) and 6% polyvinyl pyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 30°C for 60 min under the protection of an inert atmosphere, and then 1% azobisisobutyronitrile (AIBN) and 0.5 g of E-HKUST-1 were added again according to the total mass percentage of the chitosan solution and the MMA monomer, the temperature was raised to 70°C, stirred for 5 h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase Mix PCEH-1 and initiator dibenzoyl peroxide BPO, wherein the mass percentage of PCEH-1 is 99.9% and the mass percentage of BPO is 0.1%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, Preparation of Sprayable Anticorrosive Coating Liquid Phase Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone are uniformly mixed to obtain a sprayable anti-corrosion coating liquid phase; the mass percentages of the three are 97.5%, 2% and 0.5% respectively.

[0035] Step 6: Sprayable anti-corrosion coating preparation The solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at 2g / mL, and then high-pressure spraying is performed.

[0036] Embodiment 6: This embodiment can cyclically construct and deconstruct the S of the antibacterial micro-interface 2- The preparation method of the anti-corrosion coating is specifically implemented according to the following steps: Step 1, Preparation of copper-containing metal-organic framework (HKUST-1) Select copper nitrate (Cu(NO 3 ) 2 ) as the metal source and trimesic acid (BTC) as the organic ligand to prepare HKUST-1 with a specific pore structure and metal active sites. 3 ) 2and BTC were dissolved in 50 mL of N,N-dimethylformamide at a molar ratio of 0.5:1, where Cu(NO 3 ) 2 The mass fraction is 4%. The mixed solution was transferred to a reactor and reacted at 200°C for 18 hours to allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals. After the reaction, the product was washed with dimethylformamide (DMF) and ethanol alternately for 4 times to remove unreacted raw materials and impurities. Then, an activation treatment was performed at 70°C to remove the solvent molecules in the pores, and finally, HKUST-1 was obtained by vacuum drying at a vacuum drying temperature of 70°C. Step 2, Preparation of EDTA-modified HKUST-1 (E-HKUST-1) Weigh 2.5 g of EDTA, dissolve it in 50 mL of deionized water, and ultrasonically treat it for 30 minutes to completely dissolve it to obtain an EDTA solution. Weigh 10 g of HKUST-1 crystals, add them to the EDTA solution, and magnetically stir at room temperature for 24 hours to allow EDTA to fully interact with the HKUST-1 surface. After stirring, transfer the mixed solution to a centrifuge tube, centrifuge at 4000 r / min, and collect the precipitate. Wash the precipitate with deionized water 5 times and centrifuge to remove unbound EDTA. Place the washed product in a vacuum drying oven and dry it at 80°C for 24 hours to obtain EDTA surface-modified HKUST-1 (E-HKUST-1); Step 3, Preparation of polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1) Weigh 6 g of chitosan, dissolve it in 200 mL of 2% by mass acetic acid aqueous solution, and stir at room temperature until it is completely dissolved to obtain a chitosan solution. Filter with a filter membrane to remove insoluble impurities to obtain a clear chitosan solution for 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 10 g, and a water-ethanol mixed solution was added to the mixed system again, with the addition amount of water and ethanol being 100 mL, and the volume ratio being 5:1, and then 3% methyl methacrylate (MMA) and 6% polyvinyl pyrrolidone (PVP) were added according to the total mass percentage of the chitosan solution and the MMA monomer, and stirred at 40°C for 50 min under the protection of an inert atmosphere, and then 5% azobisisobutyronitrile (AIBN) and 1 g of E-HKUST-1 were added again according to the total mass percentage of the chitosan solution and the MMA monomer, the temperature was raised to 80°C, stirred for 5 h, and freeze-dried to obtain polymethyl methacrylate (PMMA) grafted chitosan (CS) copolymerized E-HKUST-1 core-shell microspheres (PCEH-1); Step 4: Preparation of the sprayable anticorrosive coating solid phase 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%, and after mixing, a sprayable anti-corrosion coating solid phase is obtained; Step 5, Preparation of Sprayable Anticorrosive Coating Liquid Phase Methyl methacrylate monomer (MMA), N,N-dimethyl-p-toluidine and hydroquinone are uniformly mixed to obtain a sprayable anti-corrosion coating liquid phase; the mass percentages of the three are 99.5%, 0.4% and 0.1% respectively.

[0037] Step 6: Sprayable anti-corrosion coating preparation The solid phase of the sprayable anti-corrosion coating and the liquid phase of the sprayable anti-corrosion coating are mixed and stirred into a fluid at a concentration of 1.5 g / mL, and then high-pressure spraying is performed.

[0038] It has been verified that after the anti-corrosion coating prepared in Examples 1-6 of the present invention was sprayed on the metal surface and co-cultured with sulfate-reducing bacteria for 30 days, there was no sign of corrosion on the metal surface, and after detection by a flame atomic spectrophotometer, no antibacterial ions were present in the culture solution. Figure 1 As shown in the figure, after taking out the samples from the culture medium at 10 days, 20 days and 30 days, the suspension containing bacterial strains was obtained by ultrasonic treatment. After coating on agar plates, no obvious colonies were produced, indicating that the coating has excellent antibacterial effect. The above results show that the S-type slurry prepared by the method of the present invention can cyclically construct and deconstruct antibacterial micro-interfaces. 2- Responsive underground anti-corrosion coatings can precisely respond to construct antibacterial microinterfaces and achieve excellent anti-corrosion effects.

Claims

1. S that can recycle and construct and deconstruct antibacterial micro-interfaces 2- The method for preparing the responsive anti-corrosion coating is characterized in that: Follow the steps below to implement it: Step 1, preparing the copper-containing metal organic framework HKUST-1; Step 2, using ethylenediaminetetraacetic acid to surface-modify the HKUST-1 obtained in step 1 to obtain E-HKUST-1; Step 3, using the E-HKUST-1 obtained in step 2 as a polymerization site, preparing core-shell polymethyl methacrylate grafted chitosan copolymer E-HKUST-1 core-shell microspheres, namely PCEH-1, by solution polymerization; Step 4, preparing a solid phase for spraying an anti-corrosion coating; Step 5, preparing a liquid phase for spraying an anti-corrosion coating; Step 6: After the solid phase and liquid phase prepared in steps 4 and 5 are mixed and stirred into a fluid at a concentration of 1-2 g / mL, high-pressure spraying is performed to obtain an anti-corrosion coating.

2. The S for recyclable construction-deconstruction of antibacterial micro-interface according to claim 1 2- The method for preparing the responsive anti-corrosion coating is characterized in that: Step 1 is as follows: Cu(NO3)2 and trimesic acid are dissolved in N,N-dimethylformamide in 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 allow the metal ions and organic ligands to self-assemble to form HKUST-1 crystals; after the reaction, the product is washed alternately with dimethylformamide and ethanol for 3-5 times to remove unreacted raw materials and impurities, and then activated at 50-70°C to remove solvent molecules in the pores, and finally vacuum dried at 50-70°C to obtain HKUST-1.

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

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

5. The S for recyclable construction-deconstruction of antibacterial micro-interface according to claim 1 2- The method for preparing the responsive anti-corrosion coating is characterized in that: Step 3 is as follows: The chitosan solution was mixed with methyl methacrylate, and then a water-ethanol mixed solution was added. Then, methylenebisacrylamide and polyvinyl pyrrolidone were added to the reaction system. Under the protection of an inert atmosphere, the mixture was stirred at 30-40° C. for 30-60 min. Then, azobisisobutyronitrile and the E-HKUST-1 obtained in step 2 were added. The mixture was heated to 70-80° C., stirred for 3-5 h, and then freeze-dried to obtain core-shell microspheres PCEH-1.

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

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

1.

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

9. The S of claim 1 for recyclable construction-deconstruction of antibacterial micro-interface 2- The method for preparing the responsive anti-corrosion coating is characterized in that: Step 4 is as follows: The PCEH-1 obtained in step 3 and the initiator dibenzoyl peroxide BPO are mixed to obtain a sprayable anti-corrosion coating solid phase, wherein the mass percentage of PCEH-1 is 99.8% to 99.9%, and the mass percentage of BPO is 0.1 to 0.2%.

10. The S for recyclable construction-deconstruction of antibacterial micro-interface according to claim 1 2- The method for preparing the responsive anti-corrosion coating is characterized in that: Step 5 is as follows: Evenly mix methyl methacrylate monomer, N,N-dimethyl-p-toluidine and hydroquinone to obtain a sprayable anti-corrosion 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%.

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