Super-hydrophobic anti-corrosion and anti-icing coating as well as preparation method and application thereof

Abstract

The invention relates to the technical field of anti-corrosion coatings, in particular to a super-hydrophobic anti-corrosion and anti-icing coating and a preparation method and application thereof.The preparation method comprises the following steps that a reaction solution containing a metal ligand, an organic ligand and an organic solvent is prepared, and a nano NH2-metal organic framework material is obtained through reaction; preparing a fluorine-containing organic solution, adding the NH2-metal organic framework material to obtain a fluorinated modified nano F-metal organic framework material, and dispersing the fluorinated modified nano F-metal organic framework material in an organic solvent to obtain an F-metal organic framework dispersion liquid; preparing an epoxy resin solution; and pouring the epoxy resin solution on a metal substrate, primarily curing at room temperature, then spraying the F-metal organic framework dispersion liquid by using a spray gun, and curing at room temperature to obtain the fluorinated metal organic framework super-hydrophobic anti-corrosion and anti-icing coating. The metal organic framework-based super-hydrophobic anti-corrosion and anti-icing coating with the passive delay anti-icing function is prepared, so that repelling and anti-icing of corrosive media (such as water and ions) are achieved.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coating technology, and in particular to a superhydrophobic anti-corrosion and anti-icing coating, its preparation method, and its application. Background Technology

[0002] Marine engineering facilities and equipment not only face corrosion problems caused by the harsh marine environment, but also the problem of surface icing in winter. The synergistic effect of corrosion and icing creates a vicious cycle: the moisture produced by melting ice accelerates the corrosion process, while the surface roughening caused by corrosion products provides more sites for ice crystal adhesion, further aggravating icing, ultimately significantly shortening the service life of metal structures and increasing maintenance costs and safety hazards.

[0003] Superhydrophobic coatings (contact angle with water >150°, roll-off angle <10°) have shown great application potential in corrosion and anti-icing fields due to their unique non-wetting and liquid-repellent properties. However, existing superhydrophobic coatings can only delay icing and cannot actively remove ice. As ice accumulates, once the superhydrophobic coating is completely covered by ice, it will lose its anti-icing effect. This greatly hinders the further development of superhydrophobic coatings in the anti-icing field. Furthermore, in complex environments such as high humidity, low temperature, and mechanical wear, micro-nano structure damage and loss of low surface energy substances are prone to occur, leading to a sharp drop in corrosion and anti-icing performance. Existing de-icing technologies such as electrothermal de-icing, mechanical de-icing, and chemical de-icing not only have the disadvantage of low efficiency but also have a corrosive effect on metals, making it difficult to effectively complement superhydrophobic coatings.

[0004] Metal-organic frameworks (MOFs) are crystalline porous materials formed by the coordination bonds between metal ions / clusters and organic ligands, providing crucial support for overcoming the technological bottlenecks of superhydrophobic coatings. They possess highly ordered pore structures and tunable chemical compositions, achieving corrosion protection through a dual mechanism of physical barrier and chemical passivation. Their nanoscale pores can precisely control the diffusion paths of corrosive media (water, oxygen, chloride ions, etc.), overcoming the traditional trade-off between barrier and permeation limitations in coatings. Furthermore, MOFs offer high designability; through ligand modification or metal center regulation, low surface energy groups can be introduced or micro / nano rough structures can be constructed, providing a structural basis for improving and stabilizing superhydrophobic properties.

[0005] However, combining superhydrophobic coatings with MOFs for marine engineering protection still faces three major challenges: First, most MOFs lack sufficient chemical and thermal stability, making them prone to framework collapse in high-salt, high-humidity marine environments, leading to a sharp drop in superhydrophobic performance. Second, the interfacial compatibility between MOFs and the polymer matrices commonly used in superhydrophobic coatings is poor, and the aggregation of micro- and nano-particles can easily cause coating defects. Third, the preparation of existing MOF-based superhydrophobic coatings largely relies on siloxane coupling agents and requires high-temperature treatment (>80℃), limiting their application range.

[0006] Therefore, developing MOF-based superhydrophobic coatings that combine high environmental stability with excellent corrosion and ice resistance has become a key technological direction that urgently needs to be broken through in the field of marine engineering protection. Summary of the Invention

[0007] The purpose of this invention is to provide a superhydrophobic anti-corrosion and anti-icing coating, its preparation method and application, to obtain a metal-organic framework-based superhydrophobic anti-corrosion and anti-icing coating with passive delayed anti-icing, so as to achieve the repulsion and anti-icing of corrosive media (such as water, ions).

[0008] To achieve the above objectives, the present invention provides a method for preparing a superhydrophobic anti-corrosion and anti-icing coating, comprising the following steps: (1) Prepare a reaction solution containing metal ligands, organic ligands and organic solvents, react the reaction solution at 50~200℃ for 24~120h to obtain the reaction product, wash and dry the reaction product to obtain nano-NH2-metal-organic framework material; (2) Prepare a fluorine-containing organic solution, then add the NH2-metal-organic framework material from step (1), impregnate and stir, wash and dry to obtain fluorinated nano-F-metal-organic framework material; (3) Disperse the nano-F-metal-organic framework material from step (2) in an organic solvent to obtain an F-metal-organic framework dispersion; (4) Prepare an organic phase reaction solution containing epoxy resin and an organic phase reaction solution containing curing agent respectively, and mix and stir at room temperature for 0.5~2h to obtain an epoxy resin solution; (5) Pour the epoxy resin solution from step (4) onto the metal substrate and allow it to cure at room temperature. Then, use a spray gun to spray the F-metal-organic framework dispersion from step (3). After curing at room temperature, a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating is obtained.

[0009] Preferably, in step (1), the concentration of the metal ligand in the reaction solution is 0.1~1 mol•L. -1 The metal ligands include one or more of zirconium tetrachloride, zirconium nitrate, ferric chloride, zinc nitrate, zinc chloride, titanium chloride, copper nitrate, nickel nitrate, nickel chloride, and tetrabutyl titanate.

[0010] Preferably, in step (1), the concentration range of the organic ligand is 0.1~1 mol•L. -1 The organic ligands include one or more of 2-aminoterephthalic acid, 3-amino-1,2,4-triazole, 5-aminotetrazole, 3-amino-4-(pyridin-4-yl)benzoic acid, and 5-(5-aminotetrazole)-1,3-phthalic acid.

[0011] Preferably, in step (1), the organic solvent includes one or more of ethanol, acetone, N,N-dimethylformamide, acetonitrile, n-hexane, ethyl acetate, dimethyl sulfoxide, and dichloromethane.

[0012] Preferably, in step (2), the concentration of the fluorine-containing organic solution is 0.1~1 mol•L. -1 The solute in the fluorinated organic solution includes one or more of the following: perfluorooctanoyl chloride, trifluoroacetyl chloride, trifluoromethanesulfonyl chloride, 2,3,4,5,6-pentafluorobenzoyl chloride, 2-fluorobenzoyl chloride, p-fluorobenzoyl chloride, 4-trifluoromethylbenzoyl chloride, 2,4-dichloro-5-fluorobenzoyl chloride, heptafluorobutyryl chloride, nonafluoropentanoyl chloride, undecafluorohexanoyl chloride, tridecafluoroheptanoyl chloride, pentadecanoyl octanoyl chloride, and heptafluorononanoyl chloride.

[0013] Preferably, in step (3), the mass concentration of the nano-F-metal-organic framework material in the F-metal-organic framework dispersion is 0.5~5 g•L. -1 .

[0014] Preferably, in step (4), the mass concentration of epoxy resin monomer in the organic phase reaction solution containing epoxy resin is 0.2~5 g•mL. -1 The epoxy resin is a bisphenol A type epoxy resin.

[0015] Preferably, in step (4), the mass concentration of the curing agent monomer in the organic phase reaction solution containing the curing agent is 0.2~5 g•mL. -1 The curing agent is one or more of diethylenetriamine, ethylenediamine, Mannich base, isophorone diamine, 1,3-cyclohexanedimethylamine, and N-aminoethylpiperazine.

[0016] A superhydrophobic anti-corrosion and anti-icing coating is prepared by the above-mentioned method for preparing a superhydrophobic anti-corrosion and anti-icing coating.

[0017] The above-mentioned superhydrophobic anti-corrosion and anti-icing coating is applied to the corrosion protection and anti-icing treatment of metal structures.

[0018] The protective mechanism of the metal-organic framework superhydrophobic anti-corrosion and anti-icing coating prepared in this invention is as follows: This invention utilizes the evaporation of organic solvents during the curing process of epoxy resin to create micron-level roughness, combined with the nanoscale roughness structure of F-metal-organic framework nanoparticles, to construct a micron-nano multi-level composite rough surface. The long fluorine chains on the surface of the F-metal-organic framework have extremely low surface energy, which works synergistically with the multi-level roughness structure. Sprayed onto the surface of a metal substrate and cured at room temperature, the macroscopic hardness of the coating is improved through mechanical interlocking effect. The secondary roughness structure is formed along the surface of the nanoparticles, and an air cushion layer is added, making the coating achieve a superhydrophobic state, effectively repelling moisture and corrosive media (such as chloride ions), and reducing the contact between water-soluble liquid media and the metal substrate.

[0019] The low surface energy and multi-level rough structure of the metal-organic framework superhydrophobic anti-corrosion and anti-icing coating of this invention reduce the adhesion between water and the coating, delay the nucleation and growth of ice crystals, and achieve a passive anti-icing effect; moreover, the coating structure is stable and can still maintain superhydrophobic properties in low-temperature environments, effectively mitigating the damage of icing to metal structures.

[0020] This invention improves the interfacial compatibility between MOFs and epoxy resin matrix through amidation grafting reaction of fluorinated organic molecules with NH2-MOFs, avoiding coating defects caused by MOF particle agglomeration; at the same time, the introduction of fluorine chains enhances the chemical and thermal stability of MOFs, preventing them from collapsing in corrosive environments and ensuring the long-term service performance of the coating.

[0021] Therefore, the present invention, by employing the above-mentioned superhydrophobic anti-corrosion and anti-icing coating, its preparation method, and its application, has the following beneficial effects: (1) The superhydrophobic anti-corrosion and anti-icing coating prepared by the present invention has excellent anti-corrosion performance, anti-icing performance and structural stability. The contact angle is >160° and the roll-off angle is <5°. After being soaked in 3.5% NaCl solution for 60 days, it still maintains high electrochemical impedance, which can effectively resist the corrosion of corrosive media and delay icing, thus solving the problem that the performance of existing coatings is easily degraded in complex environments.

[0022] (2) The present invention improves the chemical and thermal stability of MOFs through fluorination modification, while enhancing the interfacial compatibility between MOFs and epoxy resin matrix, avoiding particle agglomeration and coating defects, and ensuring the long-term service stability of coating under harsh environments.

[0023] (3) The preparation method of the present invention is simple, the preparation conditions are mild, and the spraying method is easy to realize industrial production.

[0024] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0025] Figure 1 This is a scanning electron microscope image of the surface of the Q235 steel plate in Embodiment 5 of the present invention; Figure 2 This is a scanning electron microscope image of the surface of the superhydrophobic metal-organic framework coating in Embodiment 5 of the present invention. Detailed Implementation

[0026] The present invention will be further described below with reference to the accompanying drawings and embodiments. Unless otherwise defined, the technical or scientific terms used in this invention should be understood in their ordinary sense by those skilled in the art. The features mentioned above or in the specific examples mentioned in this invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the invention and are not intended to limit the scope of the invention.

[0027] This invention provides a method for preparing a superhydrophobic, anti-corrosion, and anti-icing coating, comprising the following steps: (1) Prepare a reaction solution containing metal ligands, organic ligands and organic solvents, react the reaction solution at 50~200℃ for 24~120h to obtain the reaction product, wash and dry the reaction product to obtain nano NH2-metal-organic framework material.

[0028] (2) Prepare a fluorine-containing organic solution, then add the NH2-metal-organic framework material from step (1), impregnate and stir, wash and dry to obtain fluorinated nano-F-metal-organic framework material; make fluorine-containing organic molecules graft onto the amino groups on the surface of the NH2-metal-organic framework material through an amidation reaction to obtain a metal-organic framework material grafted with fluorine chains.

[0029] Metal-organic frameworks (MOFs) possess ordered pore structures, excellent chemical stability, and numerous modification sites. By grafting fluorine chains using reactions such as amidation, the surface energy of the coating is reduced, resulting in coatings with excellent stability and superhydrophobicity. On the one hand, superhydrophobicity can prevent electrochemical corrosion of metals by corrosive ions; on the other hand, the pore structure of the MOF itself can also block some larger corrosive substances, enabling the prepared MOF superhydrophobic coatings to achieve highly efficient anti-corrosion and anti-icing applications.

[0030] (3) Disperse the nano-F-metal-organic framework material from step (2) in an organic solvent to obtain an F-metal-organic framework dispersion.

[0031] (4) Prepare an organic phase reaction solution containing epoxy resin and an organic phase reaction solution containing curing agent respectively, and mix and stir at room temperature for 0.5~2h to obtain an epoxy resin solution.

[0032] (5) The epoxy resin solution from step (4) was poured onto the metal substrate and pre-cured at room temperature. Then, the F-metal-organic framework dispersion from step (3) was sprayed onto the substrate using a spray gun and cured at room temperature to obtain a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating. By spraying nano-F-metal-organic framework material onto the surface of epoxy resin and curing it at room temperature, a micro-nano rough structure was constructed, and a superhydrophobic anti-corrosion and anti-icing coating with ultra-low surface energy was prepared under conditions without an external heat source.

[0033] Preferably, in step (1), the concentration of the metal ligand in the reaction solution is 0.1~1 mol•L. -1 The metal ligands include one or more of zirconium tetrachloride, zirconium nitrate, ferric chloride, zinc nitrate, zinc chloride, titanium chloride, copper nitrate, nickel nitrate, nickel chloride, and tetrabutyl titanate.

[0034] Preferably, in step (1), the concentration range of the organic ligand is 0.1~1 mol•L. -1 The organic ligands include one or more of 2-aminoterephthalic acid, 3-amino-1,2,4-triazole, 5-aminotetrazole, 3-amino-4-(pyridin-4-yl)benzoic acid, and 5-(5-aminotetrazole)-1,3-phthalic acid.

[0035] Preferably, in step (1), the organic solvent includes one or more of ethanol, acetone, N,N-dimethylformamide, acetonitrile, n-hexane, ethyl acetate, dimethyl sulfoxide, and dichloromethane.

[0036] More preferably, in step (1), the washing is performed multiple times using N,N-dimethylformamide and methanol to remove unreacted monomers and impurities, and the drying is performed at 60~100℃ for 12~24h.

[0037] More preferably, the nano-NH2-metal-organic framework material in step (1) includes one of NH2-UIO-66, NH2-MIL-53, NH2-MIL-125, Mim-NH2 / MIL-101, MAF-66, USTA-100a, Ni(BPA-NH2)2, and CAU-1-NH2.

[0038] Preferably, in step (2), the concentration of the fluorine-containing organic solution is 0.1~1 mol•L. -1 The solute in the fluorinated organic solution includes one or more of the following: perfluorooctanoyl chloride, trifluoroacetyl chloride, trifluoromethanesulfonyl chloride, 2,3,4,5,6-pentafluorobenzoyl chloride, 2-fluorobenzoyl chloride, p-fluorobenzoyl chloride, 4-trifluoromethylbenzoyl chloride, 2,4-dichloro-5-fluorobenzoyl chloride, heptafluorobutyryl chloride, nonafluoropentanoyl chloride, undecafluorohexanoyl chloride, tridecafluoroheptanoyl chloride, pentadecanoyl octanoyl chloride, and heptafluorononanoyl chloride.

[0039] More preferably, in step (2), the soaking and stirring time is 8~24 h, the washing is to remove ungrafted fluorine-containing molecules by washing with organic solvent, and the drying is to dry at 60~80℃ for 8~12 h.

[0040] More preferably, the particle size of the nano-F-metal-organic framework material obtained in step (2) is 120~180nm. The combination of the nanoparticles themselves and the micron-level roughness generated by the epoxy resin adhesive layer realizes a multi-scale synergistic effect. At the same time, the low surface energy characteristics of the long fluorine chain and the superhydrophobic synergistic effect generated by the micro-nano structure make the coating static contact angle >160° and roll-off angle <5°.

[0041] Preferably, in step (3), the mass concentration of the nano-F-metal-organic framework material in the F-metal-organic framework dispersion is 0.5~5 g•L. -1 .

[0042] In a more preferred embodiment, in step (3), the dispersion is ultrasonic dispersion.

[0043] Preferably, in step (4), the mass concentration of epoxy resin monomer in the organic phase reaction solution containing epoxy resin is 0.2~5 g•mL. -1 The epoxy resin is a bisphenol A type epoxy resin.

[0044] Preferably, in step (4), the mass concentration of the curing agent monomer in the organic phase reaction solution containing the curing agent is 0.2~5 g•mL. -1 The curing agent is one or more of diethylenetriamine, ethylenediamine, Mannich base, isophorone diamine, 1,3-cyclohexanedimethylamine, and N-aminoethylpiperazine.

[0045] More preferably, in step (5), the initial curing time is 2~4h, and the room temperature curing time is 24~72h.

[0046] More preferably, in step (5), the spray gun spraying pressure is 0.3 to 0.5 MPa, the spraying distance is 10 to 20 cm, and the number of spraying times is 2 to 3.

[0047] A superhydrophobic anti-corrosion and anti-icing coating is prepared by the above-mentioned method for preparing a superhydrophobic anti-corrosion and anti-icing coating.

[0048] Even more preferably, the thickness of the superhydrophobic anti-corrosion and anti-icing coating is 50-150 μm.

[0049] The above-mentioned superhydrophobic anti-corrosion and anti-icing coating is applied to the corrosion protection and anti-icing treatment of metal structures.

[0050] The preferred application is the overall protection of cross-material composite structures such as bridges, ports, and oil and gas pipelines, with a construction window temperature of -5~45℃.

[0051] Example 1 This invention provides a superhydrophobic, anti-corrosion, and anti-icing coating, the preparation method of which includes the following steps: (1) Prepare a solution containing 0.2 mol•L-1 Zirconium tetrachloride and 0.2 mol•L -1 The reaction solution of 2-aminoterephthalic acid with N,N-dimethylformamide was reacted at 120°C for 24 h to obtain the reaction product. The reaction product was washed three times with N,N-dimethylformamide and methanol and then dried at 80°C for 24 h to obtain the NH2-metal-organic framework material NH2-UIO-66.

[0052] (2) Prepare a solution containing 1 mol•L -1 An ethanol solution of perfluorooctanoyl chloride was prepared, and then the NH2-metal-organic framework material from step (1) was added. After impregnation and stirring for 24 h, the mixture was washed three times with N,N-dimethylformamide and methanol, and dried at 80 °C for 24 h to obtain the fluorinated nano-F-metal-organic framework material UIO-66-F.

[0053] (3) The nano-F-metal-organic framework material UIO-66-F from step (2) was ultrasonically dispersed in an organic solvent to prepare a solution with a concentration of 0.5 g•L. -1 F-metal-organic framework dispersion.

[0054] (4) Prepare solutions containing 0.2 g•mL respectively. -1 The organic phase reaction solution of bisphenol A type epoxy resin and containing 0.2 g•mL -1 The organic phase reaction solution of diethylenetriamine curing agent was mixed and stirred at room temperature for 0.5 h to obtain an epoxy resin solution.

[0055] (5) Pour the epoxy resin solution from step (4) onto a Q235 steel plate and allow it to cure for 3 hours at room temperature. Then, use a spray gun to spray the F-metal-organic framework dispersion from step (3). The spray gun pressure is 0.5 MPa, the spraying distance is 15 cm, and the spraying is repeated 3 times. After curing at room temperature for 24 hours, a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating is obtained.

[0056] Testing revealed that the prepared fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating exhibited a contact angle >160°, a roll-off angle <5°, and an electrochemical impedance of 2.4 × 10⁻⁶. 11 Ω·cm 2 After being soaked in a 3.5% NaCl solution for 60 days, the electrochemical impedance still reached 3.0 × 10⁻⁶. 9 Ω·cm 2 .

[0057] Example 2 This invention provides a superhydrophobic, anti-corrosion, and anti-icing coating, the preparation method of which includes the following steps: (1) Prepare a solution containing 0.2 mol•L -1 Zirconium tetrachloride and 0.1 mol•L -1A reaction solution of 2-aminoterephthalic acid with N,N-dimethylformamide was prepared. The reaction solution was reacted at 120 °C for 24 h to obtain the reaction product. The reaction product was washed three times with N,N-dimethylformamide and methanol, and then dried at 80 °C for 24 h to obtain the NH2-metal-organic framework material NH2-UIO-66.

[0058] (2) Prepare a solution containing 1 mol•L -1 An ethanol solution of perfluorooctanoyl chloride was prepared, and then the NH2-metal-organic framework material from step (1) was added. After impregnation and stirring for 24 h, the mixture was washed three times with N,N-dimethylformamide and methanol, and dried at 80 °C for 124 h to obtain the fluorinated nano-F-metal-organic framework material UIO-66-F.

[0059] (3) The nano-F-metal-organic framework material UIO-66-F from step (2) was ultrasonically dispersed in an organic solvent to prepare a solution with a concentration of 0.5 g•L. -1 F-metal-organic framework dispersion.

[0060] (4) Prepare solutions containing 0.2 g•mL respectively. -1 The organic phase reaction solution of bisphenol A type epoxy resin and containing 0.2 g•mL -1 The organic phase reaction solution of ethylenediamine curing agent was mixed and stirred at room temperature for 0.5 h to obtain an epoxy resin solution.

[0061] (5) Pour the epoxy resin solution from step (4) onto a Q235 steel plate and cure it at room temperature for 3 hours. Then, spray the F-metal-organic framework dispersion from step (3) with a spray gun. The spray gun pressure is 0.4 MPa and the spraying distance is 15 cm. Spray twice and cure at room temperature for 24 hours to obtain a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating.

[0062] The electrochemical impedance of the prepared fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating was tested to reach 2.0 × 10⁻⁶. 11 Ω·cm 2 After being soaked in a 3.5% NaCl solution for 60 days, the electrochemical impedance still reached 1.8 × 10⁻⁶. 9 Ω·cm 2 .

[0063] Example 3 This invention provides a superhydrophobic, anti-corrosion, and anti-icing coating, the preparation method of which includes the following steps: (1) Prepare a solution containing 0.2 mol•L -1 Zirconium tetrachloride and 0.1 mol•L -1A reaction solution of 2-aminoterephthalic acid with N,N-dimethylformamide was prepared. The reaction solution was reacted at 120 °C for 24 h to obtain the reaction product. The reaction product was washed three times with N,N-dimethylformamide and methanol, and then dried at 80 °C for 24 h to obtain the NH2-metal-organic framework material NH2-UIO-66.

[0064] (2) Prepare a solution containing 1 mol•L -1 An ethanol solution of perfluorooctanoyl chloride was prepared, and then the NH2-metal-organic framework material from step (1) was added. After impregnation and stirring for 24 h, the mixture was washed three times with N,N-dimethylformamide and methanol, and dried at 80 °C for 124 h to obtain the fluorinated nano-F-metal-organic framework material UIO-66-F.

[0065] (3) The nano-F-metal-organic framework material UIO-66-F from step (2) was ultrasonically dispersed in an organic solvent to prepare a solution with a concentration of 0.5 g•L. -1 F-metal-organic framework dispersion.

[0066] (4) Prepare solutions containing 0.2 g•mL respectively. -1 The organic phase reaction solution of bisphenol A type epoxy resin and containing 0.2 g•mL -1 The organic phase reaction solution of ethylenediamine curing agent was mixed and stirred at room temperature for 0.5 h to obtain an epoxy resin solution.

[0067] (5) Pour the epoxy resin solution from step (4) onto a Q235 steel plate and cure it at room temperature for 3 hours. Then, spray the F-metal-organic framework dispersion from step (3) with a spray gun. The spray gun pressure is 0.3 MPa and the spraying distance is 15 cm. Spray twice and cure at room temperature for 24 hours to obtain a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating.

[0068] The electrochemical impedance of the obtained superhydrophobic anticorrosive coating was tested to be 7.5 × 10⁻⁶. 10 Ω·cm 2 After being soaked in a 3.5% NaCl solution for 60 days, the electrochemical impedance still reached 5.3 × 10⁻⁶. 8 Ω·cm 2 .

[0069] Example 4 This invention provides a superhydrophobic, anti-corrosion, and anti-icing coating, the preparation method of which includes the following steps: (1) Prepare a solution containing 0.2 mol•L -1 Zirconium tetrachloride and 0.1 mol•L -1A reaction solution of 2-aminoterephthalic acid with N,N-dimethylformamide was prepared. The reaction solution was reacted at 120 °C for 24 h to obtain the reaction product. The reaction product was washed three times with N,N-dimethylformamide and methanol, and then dried at 80 °C for 24 h to obtain the NH2-metal-organic framework material NH2-UIO-66.

[0070] (2) Prepare a solution containing 1 mol•L -1 An ethanol solution of perfluorooctanoyl chloride was prepared, and then the NH2-metal-organic framework material from step (1) was added. After impregnation and stirring for 24 h, the mixture was washed three times with N,N-dimethylformamide and methanol, and dried at 80 °C for 124 h to obtain the fluorinated nano-F-metal-organic framework material UIO-66-F.

[0071] (3) The nano-F-metal-organic framework material UIO-66-F from step (2) was ultrasonically dispersed in an organic solvent to prepare a solution with a concentration of 0.5 g•L. -1 F-metal-organic framework dispersion.

[0072] (4) Prepare solutions containing 0.2 g•mL respectively. -1 The organic phase reaction solution of bisphenol A type epoxy resin and containing 0.2 g•mL -1 The organic phase reaction solution of ethylenediamine curing agent was mixed and stirred at room temperature for 0.5 h to obtain an epoxy resin solution.

[0073] (5) Pour the epoxy resin solution from step (4) onto a Q235 steel plate and cure it at room temperature for 3 hours. Then, use a spray gun to spray the F-metal-organic framework dispersion from step (3). The spray gun pressure is 0.5 MPa, the spraying distance is 15 cm, and the spraying is done twice. After curing at room temperature for 24 hours, a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating is obtained.

[0074] The electrochemical impedance of the prepared superhydrophobic anticorrosive coating was tested and found to be 1.2 × 10⁻⁶. 11 Ω·cm 2 After being soaked in a 3.5% NaCl solution for 60 days, the electrochemical impedance still reached 1.5 × 10⁻⁶. 9 Ω·cm 2 .

[0075] Example 5 This invention provides a superhydrophobic, anti-corrosion, and anti-icing coating, the preparation method of which includes the following steps: (1) Prepare a solution containing 0.2 mol•L -1 Zirconium tetrachloride and 0.1 mol•L -1A reaction solution of 2-aminoterephthalic acid with N,N-dimethylformamide was prepared. The reaction solution was reacted at 120 °C for 24 h to obtain the reaction product. The reaction product was washed three times with N,N-dimethylformamide and methanol, and then dried at 80 °C for 24 h to obtain the NH2-metal-organic framework material NH2-UIO-66.

[0076] (2) Prepare a solution containing 1 mol•L -1 An ethanol solution of perfluorooctanoyl chloride was prepared, and then the NH2-metal-organic framework material from step (1) was added. After impregnation and stirring for 24 h, the mixture was washed three times with N,N-dimethylformamide and methanol, and dried at 80 °C for 124 h to obtain the fluorinated nano-F-metal-organic framework material UIO-66-F.

[0077] (3) The nano-F-metal-organic framework material UIO-66-F from step (2) was ultrasonically dispersed in an organic solvent to prepare a solution with a concentration of 0.5 g•L. -1 F-metal-organic framework dispersion.

[0078] (4) Prepare solutions containing 0.1 g•mL respectively. -1 The organic phase reaction solution of bisphenol A type epoxy resin and containing 0.1 g•mL -1 The organic phase reaction solution of ethylenediamine curing agent was mixed and stirred at room temperature for 0.5 h to obtain an epoxy resin solution.

[0079] (5) Pour the epoxy resin solution from step (4) onto a Q235 steel plate and cure it at room temperature for 3 hours. Then, spray the F-metal-organic framework dispersion from step (3) with a spray gun. The spray gun pressure is 0.4 MPa and the spraying distance is 15 cm. Spray twice and cure at room temperature for 24 hours to obtain a fluorinated metal-organic framework superhydrophobic anti-corrosion and anti-icing coating.

[0080] The electrochemical impedance of the prepared superhydrophobic anticorrosive coating was tested to be 4.7 × 10⁻⁶. 10 Ω·cm 2 After being soaked in a 3.5% NaCl solution for 60 days, the electrochemical impedance still reached 1.2 × 10⁻⁶. 8 Ω·cm 2 .

[0081] Example 6 The difference from Example 1 is that step (1) prepares a solution containing 0.1 mol•L -1 Zinc nitrate and 0.2 mol•L -1 Ethanol reaction solution of 3-amino-1,2,4-triazole.

[0082] Step (2) Prepare a solution containing 0.1 mol•L -1 Organic solution of trifluoroacetyl chloride.

[0083] Step (3) The concentration of the F-metal-organic framework dispersion is 1 g•L -1 .

[0084] In step (4), the concentration of the organic phase reaction solution of bisphenol A epoxy resin is 1 g•mL. -1 The curing agent is a Mannich base, and the concentration of the organic phase reaction solution of the curing agent is 1 g•mL. -1 Everything else is the same as in Example 1.

[0085] Example 7 The difference from Example 1 is that step (1) prepares a solution containing 0.5 mol•L -1 Zinc chloride and 0.5 mol•L -1 5-Aminotetrazole in acetone reaction solution.

[0086] Step (2) Prepare a solution containing 0.5 mol•L -1 Organic solutions of trifluoromethanesulfonyl chloride.

[0087] In step (3), the concentration of the F-metal-organic framework dispersion is 2 g•L. -1 .

[0088] In step (4), the concentration of the organic phase reaction solution of bisphenol A epoxy resin is 2 g•mL. -1 The curing agent is isophorone diamine, and the concentration of the organic phase reaction solution of the curing agent is 2 g•mL. -1 Everything else is the same as in Example 1.

[0089] Example 8 The difference from Example 1 is that step (1) prepares a solution containing 1 mol•L -1 A mixed solution of nickel nitrate and nickel chloride and 1 mol•L -1 3-Amino-4-(pyridin-4-yl)benzoic acid in acetonitrile reaction solution.

[0090] Step (2) Prepare a solution containing 1 mol•L -1 Organic solutions of 2,3,4,5,6-pentafluorobenzoyl chloride.

[0091] Step (3) The concentration of the F-metal-organic framework dispersion is 5 g•L. -1 .

[0092] In step (4), the concentration of the organic phase reaction solution of bisphenol A epoxy resin is 5 g•mL. -1 The curing agent is 1,3-cyclohexanedimethylamine, and the concentration of the organic phase reaction solution of the curing agent is 5 g•mL. -1 Everything else is the same as in Example 1.

[0093] Example 9 The difference from Example 1 is that in step (1), the metal ligand is copper nitrate, the organic ligand is 5-(5-aminotetrazolium)-1,3-phenylenediic acid, and the organic solvent is dimethyl sulfoxide.

[0094] In step (2), the solute in the fluorine-containing organic solution is 2-fluorobenzoyl chloride.

[0095] Step (4) The curing agent is N-aminoethylpiperazine. The rest is the same as in Example 1.

[0096] Comparative Example This invention provides an anti-corrosion coating, the preparation method of which includes the following steps: (1) Prepare solutions containing 0.2 g•mL respectively -1 The organic phase reaction solution of bisphenol A type epoxy resin and containing 0.2 g•mL -1 The organic phase reaction solution of ethylenediamine curing agent was mixed and stirred at room temperature for 0.5 h to obtain an epoxy resin solution.

[0097] (2) Pour the epoxy resin solution from step (1) onto a Q235 steel plate and cure it at room temperature for 24 hours.

[0098] The electrochemical impedance of the prepared anti-corrosion coating was tested and found to be 4.23 × 10⁻⁶. 9 Ω·cm 2 After soaking in 3.5% NaCl solution for 60 days, the electrochemical impedance reached 2.48 × 10⁻⁶. 7 Ω·cm 2 .

[0099] Figure 1 This is a scanning electron microscope image of the surface of the Q235 steel plate in Embodiment 5 of the present invention, which shows that it has a rough surface; Figure 2 This is a scanning electron microscope image of the surface of the superhydrophobic, anticorrosive, and anti-icing coating of the fluorinated metal-organic framework in Example 5 of the present invention. UIO-66-F nanoparticles can be found on its surface.

[0100] In summary, the superhydrophobic metal-organic framework anti-corrosion coating prepared by this invention has excellent structural stability and good long-term operational stability, as well as high anti-corrosion performance. It can significantly improve the protective life of materials in harsh corrosive environments, providing an innovative solution for corrosion control in temporary aquatic environments, marine engineering equipment, coastal infrastructure and other fields.

[0101] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a superhydrophobic anticorrosion and anti-icing coating, characterized in that: The method comprises the following steps: (1) preparing a reaction solution containing a metal ligand, an organic ligand and an organic solvent, reacting the reaction solution at 50-200 DEG C for 24-120 h to obtain a reaction product, washing and drying the reaction product to obtain a nano NH2-metal organic framework material; (2) preparing a fluorine-containing organic solution, then adding the NH2-metal organic framework material of step (1), stirring after impregnation, washing and drying to obtain a fluorinated modified nano F-metal organic framework material; (3) dispersing the nano F-metal organic framework material of step (2) in an organic solvent to obtain an F-metal organic framework dispersion; (4) respectively preparing an organic phase reaction solution containing an epoxy resin and an organic phase reaction solution containing a curing agent, mixing and stirring at room temperature for 0.5-2 h to obtain an epoxy resin solution; (5) pouring the epoxy resin solution of step (4) on a metal substrate, preliminarily curing at room temperature, then using a spray gun to spray the F-metal organic framework dispersion of step (3), and curing at room temperature to obtain a fluorinated metal organic framework super-hydrophobic corrosion-resistant and anti-icing coating.

2. The method of claim 1, wherein the method comprises: In step (1), the concentration of the metal ligand in the reaction solution is 0.1-1 mol•L -1 The metal ligand includes one or more of zirconium tetrachloride, zirconium nitrate, iron chloride, zinc nitrate, zinc chloride, titanium chloride, copper nitrate, nickel nitrate, nickel chloride, and tetrabutyl titanate.

3. The method of claim 1, wherein the method further comprises: The concentration of the organic ligand in step (1) ranges from 0.1 to 1 mol L -1 The organic ligand includes one or more of 2-amino terephthalic acid, 3-amino-1,2,4-triazole, 5-aminotetrazole, 3-amino-4-(pyridin-4-yl)benzoic acid, 5-(5-aminotetrazole)-1,3-benzenedicarboxylic acid.

4. The method for preparing a superhydrophobic anti-corrosion and anti-icing coating according to claim 1, characterized in that: In step (1), the organic solvent comprises one or more of ethanol, acetone, N,N-dimethylformamide, acetonitrile, n-hexane, ethyl acetate, dimethyl sulfoxide and dichloromethane.

5. The method for preparing a superhydrophobic anti-corrosion and anti-icing coating according to claim 1, characterized in that: The concentration of the fluorine-containing organic solution in step (2) is 0.1-1 mol•L -1 The solute of the fluorine-containing organic solution includes one or more of perfluorooctanoyl chloride, trifluoroacetyl chloride, trifluoromethanesulfonyl chloride, 2,3,4,5,6-pentafluorobenzoyl chloride, 2-fluorobenzoyl chloride, p-fluorobenzoyl chloride, 4-trifluoromethylbenzoyl chloride, 2,4-dichloro-5-fluorobenzoyl chloride, heptafluorobutyryl chloride, nonafluoropentanoyl chloride, undecafluorohexanoyl chloride, tridecafluoroheptanoyl chloride, pentadecafluorooctanoyl chloride, heptadecafluorononanoyl chloride.

6. The method for preparing a superhydrophobic anti-corrosion and anti-icing coating according to claim 1, characterized in that: In step (3), the mass concentration of the nano F-metal organic framework material in the F-metal organic framework dispersion liquid is 0.5-5 g•L -1 .

7. The method for preparing a superhydrophobic anti-corrosion and anti-icing coating according to claim 1, characterized in that: The mass concentration of the epoxy resin monomer in the organic phase reaction solution containing the epoxy resin in step (4) is 0.2-5 g•mL -1 The epoxy resin is a bisphenol A type epoxy resin.

8. The method for preparing a superhydrophobic anti-corrosion and anti-icing coating according to claim 1, characterized in that: In step (4), the mass concentration of the curing agent monomer in the organic phase reaction solution containing the curing agent is 0.2-5 g•mL -1 The curing agent is one or more of divinyltriamine, ethylenediamine, Mannich base, isophorone diamine, 1,3-cyclohexanedimethylamine, and N-aminoethylpiperazine.

9. A superhydrophobic, corrosion-protective, and ice- repellent coating, characterized in that: The super-hydrophobic corrosion-resistant and anti-icing coating is prepared by the method of any one of claims 1-8.

10. Use of a superhydrophobic anticorrosion anti-icing coating, characterized in that: The super-hydrophobic corrosion-resistant and anti-icing coating of claim 9 is applied to metal structure corrosion protection and anti-icing treatment.

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