Anti-corrosion material and application

Abstract

The invention belongs to the technical field of metal material surface treatment, and relates to an anti-corrosion material and application thereof.A molecular cage ligand and a hydrophobic functional group are used for preparing a molecular cage-coated copper complex anti-corrosion material, and after the molecular cage-coated copper complex anti-corrosion material is used for passivating copper foil, the copper foil is subjected to surface treatment to obtain the anti-corrosion material. A composite passivation layer with a multi-stage protection structure is formed on the surface of a copper base material, a coordination network formed by a molecular cage framework and copper ions serves as an inner layer protection structure of the composite passivation layer, and hydrophobic groups grafted on the periphery form an outer layer barrier. The preparation method can be implemented under the conditions of normal temperature and normal pressure, complex equipment is not needed, process parameters are easy to control, the oxidation corrosion resistance of the passivated copper base material is remarkably improved while the original conductivity of the passivated copper base material is kept, and the preparation method has remarkable industrial application value in the field of copper material oxidation resistance.

Description

Technical Field

[0001] The invention belongs to the field of metal material surface treatment and relates to an anti-corrosion material and application thereof. Background Art

[0002] In biological microenvironments, a variety of trace or ultra-trace active species (such as free radicals, metal ions, etc.) play a key role in regulating biological processes and participate in different physiological functions. Maintaining the stability of these active species is essential for the normal operation of biological systems. At the same time, in the field of chemistry and materials science, how to construct artificial microenvironments with atomic-level resolution to stabilize active species has become one of the research hotspots.

[0003] Copper, as one of the most widely used base metals in human history, has excellent electrical conductivity (second only to silver), thermal conductivity and ductility. Among them, monovalent copper Cu(I) materials have attracted much attention in functional material research due to their unique properties in catalysis, luminescence, chemical sensing and other fields as well as good economy. However, Cu(I) has obvious defects in oxidation stability, especially in the presence of water or oxygen, it is easily oxidized to divalent copper Cu(II), which seriously limits its practical application. In order to improve the antioxidant capacity of Cu(I) and stabilize its redox state, porous materials with superhydrophobic microenvironment are usually used in the existing technology to encapsulate and protect it. Although this strategy has made some progress, the long-term stability problem of Cu(I) has not been fundamentally solved, and there is an urgent need to develop more efficient and stable Cu(I) protection technology. Summary of the invention

[0004] As a new type of porous material, organic molecular cages have shown important application potential in the field of functional materials due to their permanent cavity structure and adjustable solubility. This type of material is constructed by covalent bonding of carbon-carbon bonds or carbon-heteroatoms (such as imine bonds, borate bonds, and amide bonds). Its structural characteristics are mainly reflected in three aspects: (1) the cavity size can be precisely controlled; (2) the geometric configuration can be directed and designed; (3) the stereoelectronic environment can be programmably modified. This multi-parameter adjustable property enables organic molecular cages to construct customized molecular recognition cavities that are highly matched with the target function. It is particularly worth noting that organic molecular cages can achieve the following two functions through their unique cavity structure: (1) selective encapsulation of specific guest molecules; (2) effective shielding of highly active species. These characteristics provide new solutions to the technical bottlenecks of traditional materials in molecular recognition and active species stabilization.

[0005] In view of the above, the present invention provides an anti-corrosion material and application. Through the synergistic effect of molecular cage ligands and hydrophobic functional groups, a composite passivation layer with a multi-level protection structure is constructed on the surface of copper foil, which significantly improves the antioxidant performance of the copper foil surface. The copper foil after passivation treatment can stably exist in 0.1 M NaOH solution for more than one week, and there is no obvious change on the surface of the copper foil.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] The first aspect of the present invention provides an anti-corrosion material, comprising an organic molecular cage, a hydrophobic compound and an organic solvent, wherein the organic molecular cage is A 3 T 2 Molecular cage (C 36 N 8 H 42 ) or D 3 T 2 Molecular cage (C 36 N 8 H 42 ), the mass ratio of the organic molecular cage to the hydrophobic compound is 90-100:115-130, and the hydrophobic compound is one or more of sodium tetraphenylborate, potassium tetraphenylborate, and ammonium tetraphenylborate.

[0008] Preferably, the ratio of the mass of the organic molecular cage to the volume of the organic solvent is 90-100 mg: 5-20 mL.

[0009] Preferably, the organic solvent is two or more of chloroform, acetonitrile, ethanol, dichloromethane, methanol, and propanol. Further preferably, the organic solvent is a mixture of chloroform, acetonitrile, and ethanol in a volume ratio of 3-8:18-22:2-5.

[0010] Preferably, the A 3 T 2 The preparation method of the molecular cage is as follows: dissolving isophthalaldehyde powder in acetonitrile to obtain an aldehyde solution; dissolving tris(2-aminoethyl)amine in acetonitrile to obtain an amine solution; injecting the amine solution into the aldehyde solution, stirring, and performing an amine-aldehyde condensation reaction. After the reaction is completed, the target product powder is obtained, and the powder is washed and dried to obtain A 3 T 2Molecular cage. Further preferably, 530-1100 mg of isophthalaldehyde is dissolved in 30-70 mL of acetonitrile to obtain the aldehyde solution; 400-800 µL of tris(2-aminoethyl)amine is dissolved in 5-200 mL of acetonitrile to obtain the amine solution; the amine solution is injected into the aldehyde solution, stirred at 0-25 °C for 20-72 h, and an amine-aldehyde condensation reaction is performed. After the reaction is completed, a target product white powder is obtained, which is washed 3-5 times with 10-30 mL of acetonitrile and dried at 0-40 °C to obtain A 3 T 2 Molecular cage.

[0011] Preferably, the D 3 T 2 The preparation method of the molecular cage is as follows: dissolving terephthalaldehyde powder in dichloromethane to obtain an aldehyde solution; dissolving tris(2-aminoethyl)amine in dichloromethane to obtain an amine solution; injecting the amine solution into the aldehyde solution, stirring, and performing an amine-aldehyde condensation reaction. After the reaction is completed, the target product powder is obtained, and the D 3 T 2 Molecular cage. Further preferably, 530-1100 mg of terephthalaldehyde is dissolved in 30-70 mL of dichloromethane to obtain the aldehyde solution; 400-800 µL of tris(2-aminoethyl)amine is dissolved in 5-200 mL of acetonitrile to obtain the amine solution; the amine solution is injected into the aldehyde solution, stirred at 0-25 °C for 20-72 h, and an amine-aldehyde condensation reaction is performed. After the reaction is completed, a light yellow powder of the target product is obtained, which is washed 3-5 times with 10-30 mL of dichloromethane and dried at 0-40 °C to obtain D 3 T 2 Molecular cage.

[0012] Preferably, the method for preparing the anti-corrosion material comprises: mixing the organic molecular cage, the hydrophobic compound and the organic solvent in proportion, ultrasonically treating the mixture, and then filtering the mixture to obtain a uniformly dispersed molecular cage-coated copper complex anti-corrosion material.

[0013] Preferably, the ultrasonic treatment lasts for 10-20 min, the temperature is 0-30° C., and the filtration is performed using an organic filter membrane.

[0014] The second aspect of the present invention provides the use of the anti-corrosion material in the anti-oxidation corrosion of copper materials.

[0015] Preferably, the application method is: uniformly coating the anti-corrosion material on the surface of the pre-treated copper foil for passivation treatment.

[0016] Preferably, the pretreatment comprises the following steps: ultrasonically cleaning oxides on the surface of the copper foil with an ethanol solution containing 1-2 wt % acetic acid, and then cleaning organic matter on the surface with isopropanol.

[0017] Preferably, the specific operation steps of the coating are: dripping the anti-corrosion material on one end of the copper foil, using a 5-100µm precision wire rod, applying constant pressure in a constant temperature environment of 25±2°C, pulling the wire rod at a constant speed, ensuring that the wire rod maintains complete linear contact with the surface of the copper foil, so that the coating liquid is evenly spread on the surface of the copper foil, and standing for 10~15 minutes.

[0018] Preferably, the size of the copper foil is 2 cm×2 cm, and the thickness of the copper foil is 10 μm.

[0019] Preferably, 70-90 μL of the anti-corrosion material is used per 4 square centimeters of copper foil surface.

[0020] The molecular cage-coated copper complex anti-corrosion material prepared by the present invention is coated on the surface of copper foil, and a coordination chemical reaction occurs between the organic molecular cage structure and the surface of the copper foil, thereby forming a dense nanoscale coordination protective layer in situ on the surface of the copper foil. The organic molecular cage acts as a functional ligand, and effectively stabilizes the copper (I) ions inside the cage-like framework through its cavity structure. At the same time, a hydrophobic protective layer is constructed on the periphery of the molecular cage by introducing hydrophobic counter ions, thereby forming a double protection mechanism from the inside to the outside: the inner molecular cage coordination protective layer can stabilize the valence state of the copper (I) ions, and the outer hydrophobic groups can block oxygen and moisture in the environment. This synergistic protection effect significantly improves the anti-oxidation performance of the copper foil surface, allowing it to maintain excellent conductivity and surface integrity in high temperature and high humidity environments.

[0021] The advantages and beneficial effects of the present invention are:

[0022] (1) The present invention uses isophthalaldehyde, terephthalaldehyde and tri(2-aminoethyl)amine as precursors to synthesize an organic cage A through an imine condensation reaction. 3 T 2 and D 3 T 2 After the prepared anti-corrosion material passivates the surface of the copper foil, a composite passivation layer with a multi-level protection structure is formed on the surface of the copper foil. The composite passivation layer is composed of a coordination network formed by a molecular cage skeleton and copper ions as an inner layer protection structure, and the hydrophobic groups grafted on the periphery constitute an outer layer barrier. Through the synergistic effect of the molecular cage ligands and the hydrophobic counterions, the antioxidant and corrosion resistance of the copper foil surface is significantly improved. Even in alkaline solutions, it can be stably present for more than a week, avoiding the use of potentially toxic materials such as precious metals.

[0023] (2) The copper foil after passivation treatment of the present invention not only has high antioxidant capacity, but also maintains the original conductivity of the copper foil, and can be used in the field of conductive materials and conductive films.

[0024] (3) The preparation method of the anti-corrosion material of the present invention is simple, the reaction conditions are mild, it is environmentally friendly, and the cost is low. It can be used for the anti-oxidation and anti-corrosion treatment of various copper materials at room temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the SEM image of the copper foil after pretreatment.

[0026] Figure 2 This is the SEM image of the copper foil after passivation in Application Example 1.

[0027] Figure 3 This is the SEM image of the pretreated copper foil after being immersed in 0.1M sodium hydroxide solution and corroded for 1 week.

[0028] Figure 4 This is the SEM image of the passivated copper foil in Application Example 1 after being immersed in 0.1M sodium hydroxide solution and corroded for one week.

[0029] Figure 5 This is a SEM image of the thickness of the thin film formed on the surface of the copper foil after passivation in Application Example 1.

[0030] Figure 6 The conductivity test diagram of the pretreated copper foil and the passivated copper foil in Application Example 1 before and after corrosion in a 0.1M sodium hydroxide solution;

[0031] Figure 7 The Raman spectra of the pretreated copper foil, the passivated copper foil of Application Example 1, and the passivated copper foil of Comparative Application Examples 1 to 3 after being immersed in 0.1M sodium hydroxide solution for one week. DETAILED DESCRIPTION

[0032] The present invention is described in detail below through a plurality of exemplary embodiments. It should be particularly pointed out that the specific embodiments described herein are only used to more clearly illustrate the technical solution of the present invention, and do not constitute any limitation on the protection scope of the present invention. For the numerical range mentioned in the present invention, it should be understood as the intermediate value between the upper limit and the lower limit of the specific range involved, and the boundary value of the above sub-range can be selectively included or excluded in the sub-range. It is particularly noted that even if certain intermediate values ​​or sub-ranges are not explicitly listed in the specification, these values ​​and ranges should still be deemed to have been fully disclosed and included in the protection scope of the present invention. Those skilled in the art should understand that any reasonable changes or adjustments based on the disclosed numerical range, as long as its numerical point or sub-range falls within the originally disclosed numerical range, should belong to the protection scope of the present invention.

[0033] Example 1

[0034] A corrosion-resistant material, the preparation method comprising the following steps:

[0035] (1) A 3 T 2 The preparation method of the molecular cage is as follows: 530 mg of isophthalaldehyde is dissolved in 30 mL of acetonitrile to obtain an aldehyde solution; 400 µL of tris(2-aminoethyl)amine is dissolved in 5 mL of acetonitrile to obtain an amine solution; the amine solution is injected into the aldehyde solution, the reaction temperature is 25°C, and the mixture is stirred for 30 hours to perform an amine-aldehyde condensation reaction. After the reaction is completed, the mixture is washed 3-5 times with 30 mL of acetonitrile, and dried at 40°C to obtain a white powder, namely A. 3 T 2 Molecular cage (C 36 N 8 H 42 ), the molecular structure is shown in Formula I.

[0036] Formula Ⅰ.

[0037] (2) Weigh 96 mg of A 3 T 2 The molecular cage and 120 mg of sodium tetraphenylborate were dissolved in 10 mL of a mixture of chloroform, acetonitrile and ethanol (the volume ratio of chloroform, acetonitrile and ethanol in the mixture was 5:20:3), ultrasonicated at 25°C for 15 min to fully dissolve it, and then filtered using an organic filter membrane to obtain a uniformly dispersed molecular cage-coated copper complex anti-corrosion material.

[0038] Application Example 1

[0039] Application of anti-corrosion materials in anti-oxidation corrosion of copper materials:

[0040] (1) Take a 2 cm × 2 cm copper foil (thickness 10 µm), use an ethanol solution containing 1 wt% acetic acid to ultrasonically clean the oxide on the surface of the copper foil, and then use isopropanol to clean the organic matter on the surface to obtain the pretreated copper foil, which is stored in isopropanol for later use;

[0041] (2) Place the pretreated copper foil flatly on a clean glass substrate, and evenly apply the molecular cage-coated copper complex anti-corrosion material prepared in Example 1 on the surface of the pretreated copper foil for passivation treatment. The specific operation is: use a pipette to accurately measure 80 µL of the molecular cage-coated copper complex anti-corrosion material and drip it on one end of the copper foil. Select a 50 µm precision wire rod, apply constant pressure in a constant temperature environment of 25±2°C, and pull the wire rod at a uniform speed to ensure that the wire rod maintains complete linear contact with the surface of the copper foil, so that the molecular cage-coated copper complex anti-corrosion material is evenly spread on the surface of the copper foil, let it stand for 10 minutes, wait for the solvent to fully evaporate, turn the copper foil over, and perform the same passivation treatment on the other side of the copper foil, and finally obtain a double-sided passivated copper foil.

[0042] The pretreated copper foil and the passivated copper foil were scanned by electron microscope, and the SEM images are as follows: Figure 1 and Figure 2 As shown, it can be seen that Figure 1 The surface of the copper foil after pretreatment is smooth. Figure 2 A thin film is formed on the surface of the passivated copper foil.

[0043] The pretreated copper foil and the passivated copper foil were respectively immersed in 0.1M NaOH solution for corrosion for 1 week and then scanned by electron microscope. The SEM images are shown in the figure below. Figure 3 and Figure 4 As shown by Figure 3 It can be seen that the surface of the copper foil after pretreatment shows obvious oxidation corrosion morphology. The surface of the copper foil is rough with many oxide particles, and the roughness increases significantly. Figure 4 It can be seen that the surface morphology of the copper foil passivated with the anti-corrosion material of the molecular cage-coated copper complex of the present invention after being immersed in the same conditions is different from that before immersion ( Figure 2 ), which proves that after the copper complex anti-corrosion material of the present invention is coated on the surface of the copper foil, a composite passivation layer with a multi-level protection structure is formed on the surface of the copper substrate, which significantly improves the antioxidant properties of the copper foil and can still maintain excellent surface stability in an alkaline environment.

[0044] The thickness of the film formed on the surface of the passivated copper foil is shown in the SEM image. Figure 5 As shown, it can be seen that the thickness of the passivation layer is about 50 nm.

[0045] The pretreated copper foil and the copper foil after passivation in Example 1 were respectively immersed in 0.1M sodium hydroxide solution for corrosion for 1 week, and then the conductivity test was performed. The results are as follows: Figure 6 As shown, it can be seen that the conductivity of the pretreated copper foil is significantly reduced after corrosion, and the conductivity decrease is relatively low after corrosion of the passivated copper foil in Application Example 1.

[0046] Example 2

[0047] A corrosion-resistant material, the preparation method comprising the following steps:

[0048] (1) D 3 T 2 Preparation method of molecular cage: 530 mg of terephthalaldehyde is dissolved in 30 mL of dichloromethane to obtain an aldehyde solution; 400 µL of tris(2-aminoethyl)amine is dissolved in 5 mL of dichloromethane to obtain an amine solution; the amine solution is injected into the aldehyde solution, the reaction temperature is 25°C, stirred for 30 hours, and an amine-aldehyde condensation reaction is carried out. After the reaction is completed, it is washed 3-5 times with 30 mL of dichloromethane and dried at 40°C to obtain a light yellow powder, namely D 3 T 2 Molecular cage (C36 N 8 H 42 ), the molecular structure is shown in Formula II.

[0049] Formula II.

[0050] (2) Weigh 96 mg of D 3 T 2 The molecular cage and 120 mg of sodium tetraphenylborate were dissolved in 10 mL of a mixture of chloroform, acetonitrile and ethanol (the volume ratio of chloroform, acetonitrile and ethanol in the mixture was 5:20:3), ultrasonicated at 25°C for 20 min to fully dissolve it, and then filtered using an organic filter membrane to obtain a uniformly dispersed molecular cage-coated copper complex anti-corrosion material.

[0051] Application Example 2

[0052] The treatment method is the same as that in Example 1. After the prepared double-sided passivated copper foil was immersed in 0.1M NaOH solution for corrosion for 7 days, its surface morphology did not change significantly compared with that before the treatment.

[0053] Comparative Example 1

[0054] The only difference from Example 1 is that in step (2), 96 mg of A 3 T 2 The molecular cage is dissolved in 10 ml of chloroform and fully dissolved by ultrasonication. The solution is then filtered to obtain a copper complex anti-corrosion material for later use.

[0055] Comparative application example 1

[0056] The copper foil was passivated using the copper complex anti-corrosion material prepared in Comparative Example 1. The treatment method was the same as that in Application Example 1 to prepare a double-sided passivated copper foil.

[0057] Comparative Example 2

[0058] The preparation method of the corrosion-resistant material is as follows: 120 mg of sodium tetraphenylborate is dissolved in 10 ml of a mixture of acetonitrile and ethanol (the volume ratio of acetonitrile to ethanol in the mixture is 20:3), ultrasonically dissolves it fully, and then filters the solution to obtain the corrosion-resistant material for later use.

[0059] Comparative Application Example 2

[0060] The anti-corrosion material prepared in Comparative Example 2 was used to passivate the copper foil, and the treatment method was the same as that in Application Example 1 to prepare a double-sided passivated copper foil.

[0061] Comparative Example 3

[0062] The only difference from Example 1 is that the molecular cage uses RA3 T 2 Molecular cage (C 36 N 8 H 54 ), the molecular structure is shown in Formula III.

[0063] Formula III.

[0064] RA 3 T 2 The preparation method of the molecular cage is:

[0065] (1) Preparation A 3 T 2 Molecular cage, prepared by the same method as in Example 1;

[0066] (2) Add 300 mg of A 3 T 2 The molecular cage was dissolved in a mixture of dichloromethane and methanol in a volume ratio of 1:1, and 300 mg NaBH 4 The reaction was stirred at room temperature for 15 h, and then 1 mL of water was added and the solution was stirred for another 9 h. The solution was removed by rotary evaporation. 10 ml of water and 10 ml of dichloromethane were added for extraction, and the product was vacuum dried at 40 °C for 24 h to obtain the reduced molecular cage RA 3 T 2 .

[0067] Comparative Application Example 3

[0068] The anti-corrosion material prepared in Comparative Example 3 was used to passivate the copper foil, and the treatment method was the same as that in Application Example 1 to prepare a double-sided passivated copper foil.

[0069] The passivated copper foils of Application Examples 1-2 and Comparative Application Examples 1-3 were respectively immersed in 0.1M sodium hydroxide solution for corrosion for 1 week, and then Raman spectroscopy analysis was performed. The Raman spectra are as follows: Figure 7 As shown in the figure, it can be seen that the copper foils treated by passivation in application examples 1 to 2 do not have a peak of copper oxide, while the copper foils treated by passivation in application examples 1 to 3 have a peak at 150 cm -1 、290 cm -1 、335 cm -1 、628 cm -1 Raman peaks appear at these locations, which are attributed to Cu 2 O and CuO substances.

[0070] The present invention describes the technical scheme in detail through the above-mentioned embodiments, but it should be understood that these specific implementations are only used to illustrate the technical concept of the present invention, and do not limit the protection scope of the present invention. Within the basic concept of the technical scheme of the present invention, those skilled in the art can make various appropriate modifications and variations thereto, and these modifications and variations should all be included in the protection scope of the present invention. It should be particularly noted that the various technical features described in this specification can be combined in any feasible way without causing technical contradictions. For the sake of simplicity, this specification does not list all possible combinations one by one. In addition, different implementations of the present invention can also be combined arbitrarily, as long as the combination does not deviate from the core inventive concept of the present invention, it should be regarded as the technical content disclosed by the present invention.

Claims

1. A corrosion-resistant material, characterized in that: It includes an organic molecular cage, a hydrophobic compound and an organic solvent, wherein the organic molecular cage is an A3T2 molecular cage or a D3T2 molecular cage, the mass ratio of the organic molecular cage to the hydrophobic compound is 90-100:115-130, and the hydrophobic compound is one or more of sodium tetraphenylborate, potassium tetraphenylborate and ammonium tetraphenylborate.

2. The anti-corrosion material according to claim 1, characterized in that: The ratio of the mass of the organic molecular cage to the volume of the organic solvent is 90-100 mg: 5-20 mL.

3. The anti-corrosion material according to claim 1, characterized in that: The organic solvent is two or more of chloroform, acetonitrile, ethanol, dichloromethane, methanol and propanol.

4. The anti-corrosion material according to claim 3, characterized in that: The organic solvent is prepared by mixing chloroform, acetonitrile and ethanol in a volume ratio of 3-8:18-22:2-5.

5. The anti-corrosion material according to claim 1, characterized in that: The preparation method of the A3T2 molecular cage is as follows: dissolving isophthalaldehyde powder in acetonitrile to obtain an aldehyde solution; dissolving tri(2-aminoethyl)amine in acetonitrile to obtain an amine solution; injecting the amine solution into the aldehyde solution, stirring, and performing an amine-aldehyde condensation reaction. After the reaction is completed, a target product powder is obtained, and the A3T2 molecular cage is obtained after washing and drying.

6. The anti-corrosion material according to claim 1, wherein the preparation method of the D3T2 molecular cage is: dissolving terephthalaldehyde powder in dichloromethane to obtain an aldehyde solution; dissolving tris(2-aminoethyl)amine in dichloromethane to obtain an amine solution; injecting the amine solution into the aldehyde solution, stirring, and performing an amine-aldehyde condensation reaction. After the reaction is completed, a target product powder is obtained, which is washed and dried to obtain a D3T2 molecular cage.

7. Use of the anti-corrosion material according to any one of claims 1 to 6 in anti-oxidation corrosion of copper materials.

8. The use according to claim 7, characterized in that: The application method is: evenly apply the anti-corrosion material to the surface of the pre-treated copper foil for passivation treatment.

9. The use according to claim 8, characterized in that: The pretreatment The method comprises the following steps: using an ethanol solution containing 1-2 wt% acetic acid to ultrasonically clean the oxide on the surface of the copper foil, and then using isopropanol to clean the organic matter on the surface; The specific operation steps of the coating are: dripping the anti-corrosion material on one end of the copper foil, using a precision wire rod, applying constant pressure in a constant temperature environment of 25±2°C, pulling the wire rod at a constant speed, ensuring that the wire rod and the surface of the copper foil maintain complete linear contact, so that the coating liquid is evenly spread on the surface of the copper foil, and standing for 10~15 minutes.

10. The use according to claim 8, characterized in that: Use 20~30 µL of the anti-corrosion material per square centimeter of copper foil surface.

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