An anti-corrosion material and its application

Abstract

The present invention belongs to the technical field of surface treatment of metal materials, and relates to an anti-corrosion material and its application. By using a molecular cage ligand and a hydrophobic functional group to prepare a molecular cage-coated copper complex anti-corrosion material, after passivating a copper foil with the molecular cage-coated copper complex anti-corrosion material, a composite passivation layer with a multi-level protection structure is formed on the surface of the copper substrate. The composite passivation layer has a coordination network formed by the molecular cage skeleton and copper ions as the inner protection structure, and the outer grafted hydrophobic groups constitute the outer barrier. The preparation method of the present invention can be implemented under normal temperature and pressure conditions, without complex equipment, and the process parameters are easy to control. Moreover, the passivated copper substrate not only maintains its original electrical conductivity but also significantly improves its anti-oxidation and corrosion resistance, having significant industrial application value in the field of copper material anti-oxidation.

Description

Technical Field

[0001] The present invention belongs to the field of surface treatment of metal materials, and relates to a corrosion-resistant material and its application. Background Art

[0002] In the biological microenvironment, a variety of trace or ultra-trace reactive species (such as free radicals, metal ions, etc.) play a key role in regulating biological processes and are involved in different physiological functions. Maintaining the stability of these reactive species is crucial for the normal operation of biological systems. At the same time, in the fields of chemistry and materials science, how to construct an artificial microenvironment with atomic-level resolution to stabilize reactive 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 the research of functional materials due to their unique properties and good economy in the fields of catalysis, luminescence, chemical sensing, etc. However, Cu(I) has obvious defects in oxidation stability, especially in an environment with the presence of water or oxygen, it is easily oxidized to divalent copper Cu(II), which seriously limits its practical applications. To improve the antioxidant ability of Cu(I) and stabilize its redox state, porous materials with a superhydrophobic microenvironment are usually used to encapsulate and protect it in the prior art. Although certain progress has been made in this strategy, the long-term stability problem of Cu(I) has not been fundamentally solved, and it is urgent to develop more efficient and stable Cu(I) protection technologies. Summary of the Invention

[0004] As a new type of porous material, organic molecular cages show important application potential in the field of functional materials due to their permanent cavity structure and adjustable solubility. These materials are constructed by covalent connection through carbon-carbon bonds or carbon-heteroatom (such as imine bonds, borate bonds, and amide bonds, etc.). Their structural characteristics are mainly reflected in three aspects: (1) the cavity size can be precisely regulated; (2) the geometric configuration can be designed directionally; (3) the stereo-electronic environment can be modified programmatically. This multi-parameter adjustable property enables organic molecular cages to construct customized molecular recognition cavities that highly match the target functions. It is particularly worth noting that through its unique cavity structure, organic molecular cages can achieve the following two functions: (1) selectively encapsulating specific guest molecules; (2) effectively shielding highly reactive species. These characteristics provide new solutions to the technical bottlenecks existing in traditional materials in molecular recognition and reactive species stabilization.

[0005] In view of the above, the present invention provides an anti-corrosion material and its application. Through the synergistic effect of the molecular cage ligand and the hydrophobic functional group, a composite passivation layer with a multi-level protection structure is constructed on the surface of the copper foil, significantly improving the antioxidant performance of the copper foil surface. The passivated copper foil can stably exist in a 0.1 M NaOH solution for more than 1 week, and there is no obvious change on the surface of the copper foil.

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

[0007] In the first aspect of the present invention, an anti-corrosion material is provided, which comprises an organic molecular cage, a hydrophobic compound and an organic solvent. The organic molecular cage is an A3T2 molecular cage (C 36 N8H 42 ) or a D3T2 molecular cage (C 36 N8H 42 ). The mass ratio of the organic molecular cage to the hydrophobic compound is 90-100:115-130. 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 composed of chloroform, acetonitrile, and ethanol mixed in a volume ratio of 3-8:18-22:2-5.

[0010] Preferably, the preparation method of the A3T2 molecular cage is as follows: Dissolve isophthalaldehyde powder in acetonitrile to obtain an aldehyde solution; dissolve tris(2-aminoethyl)amine in acetonitrile to obtain an amine solution; inject the amine solution into the aldehyde solution, stir, and carry out an amine-aldehyde condensation reaction. After the reaction is completed, obtain the target product powder, wash and dry to obtain the A3T2 molecular cage. Further preferably, dissolve 530-1100 mg of isophthalaldehyde in 30-70 mL of acetonitrile to obtain the aldehyde solution; dissolve 400-800 μL of tris(2-aminoethyl)amine in 5-200 mL of acetonitrile to obtain the amine solution; inject the amine solution into the aldehyde solution, stir at 0-25 °C for 20-72 h to carry out the amine-aldehyde condensation reaction. After the reaction is completed, obtain the target product white powder, wash 3-5 times with 10-30 mL of acetonitrile, and dry at 0-40 °C to obtain the A3T2 molecular cage.

[0011] Preferably, the preparation method of the D3T2 molecular cage is as follows: Dissolve terephthalaldehyde powder in dichloromethane to obtain an aldehyde solution; dissolve tris(2-aminoethyl)amine in dichloromethane to obtain an amine solution; inject the amine solution into the aldehyde solution, stir, and carry out an amine-aldehyde condensation reaction. After the reaction ends, obtain the target product powder, and obtain the D3T2 molecular cage after washing and drying. Further preferably, dissolve 530-1100 mg of terephthalaldehyde in 30-70 mL of dichloromethane to obtain the aldehyde solution; dissolve 400-800 µL of tris(2-aminoethyl)amine in 5-200 mL of acetonitrile to obtain the amine solution; inject the amine solution into the aldehyde solution, stir at 0-25 °C for 20-72 h to carry out the amine-aldehyde condensation reaction. After the reaction ends, obtain the light yellow powder of the target product, wash it 3-5 times with 10-30 mL of dichloromethane, and obtain the D3T2 molecular cage after drying at 0-40 °C.

[0012] Preferably, the preparation method of the anti-corrosion material includes: mixing an organic molecular cage, a hydrophobic compound, and an organic solvent in proportion and then performing ultrasonic treatment, and then filtering to obtain a uniformly dispersed anti-corrosion material of a molecular cage-coated copper complex.

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

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

[0015] Preferably, the application method is as follows: Uniformly coat the anti-corrosion material on the surface of the pretreated copper foil and perform passivation treatment.

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

[0017] Preferably, the specific operation steps of the coating are as follows: Drop the anti-corrosion material at one end of the copper foil, use a 5-100 µm precision wire bar, apply a constant pressure in a constant temperature environment of 25±2 °C, and pull the wire bar at a uniform speed to ensure that the wire bar is in 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 let it stand for 10-15 min.

[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 on the surface of every 4 square centimeters of copper foil.

[0020] The corrosion-resistant material of copper complex coated with molecular cages prepared by the present invention is coated on the surface of copper foil. Through the coordination chemical reaction between the organic molecular cage structure and the surface of copper foil, a dense nano-scale coordination protection layer is formed in-situ on the surface of copper foil. As a functional ligand, the organic molecular cage effectively stabilizes copper(I) ions inside the cage framework through its cavity structure. Meanwhile, a hydrophobic protection layer is constructed around the molecular cage by introducing hydrophobic counterions, thus forming a double protection mechanism from the inside out: the inner molecular cage coordination protection layer can stabilize the valence state of copper(I) ions, and the outer hydrophobic groups can block oxygen and moisture in the environment. This synergistic protection effect significantly improves the antioxidant performance of the copper foil surface, enabling it to maintain excellent electrical conductivity and surface integrity even in high-temperature and high-humidity environments.

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

[0022] (1) Using isophthalaldehyde, terephthalaldehyde and tris(2-aminoethyl)amine as precursors, the organic cages A3T2 and D3T2 are synthesized through imine condensation reaction. After passivating the surface of copper foil with the prepared corrosion-resistant material, a composite passivation layer with a multi-level protection structure is formed on the surface of copper foil. The composite passivation layer has a coordination network formed by the molecular cage skeleton and copper ions as the inner protection structure, and the grafted hydrophobic groups on the periphery constitute the outer barrier. Through the synergistic effect of the molecular cage ligand and the hydrophobic counterions, the antioxidant and corrosion-resistant performance of the copper foil surface is significantly improved, and it can stably exist for more than one week even in alkaline solutions, 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 ability but also maintains the original electrical conductivity of the copper foil, and can be used in the fields of conductive materials and conductive films.

[0024] (3) The preparation method of the corrosion-resistant material of the present invention is simple, the reaction conditions are mild, it is environmentally friendly and low in cost, and it can be used for antioxidant and corrosion-resistant treatment of various copper materials at room temperature. Description of the Drawings

[0025] Figure 1 It is the SEM image of the pretreated copper foil.

[0026] Figure 2 It is the SEM image of the passivated copper foil in Application Example 1.

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

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

[0029] Figure 5 SEM image of the thickness of the film formed on the surface of the copper foil passivated in Application Example 1.

[0030] Figure 6 Conductivity test diagrams of the pre-treated copper foil and the copper foil passivated in Application Example 1 before and after corrosion in 0.1 M sodium hydroxide solution;

[0031] Figure 7 Raman spectra of the pre-treated copper foil, the copper foil passivated in Application Example 1, and the copper foils passivated in Comparative Application Examples 1 - 3 after being immersed in 0.1 M sodium hydroxide solution for 1 week. Detailed implementation manners

[0032] The present invention will be described in detail below through multiple exemplary embodiments. It should be particularly noted that the specific implementation manners described herein are only used to more clearly illustrate the technical solutions of the present invention and do not constitute any limitation to the protection scope of the present invention. For the numerical ranges mentioned in the present invention, they should be understood as the intermediate values between the upper and lower limits of the specific ranges involved, and the boundary values of the above sub-ranges can be selectively included or excluded within the sub-ranges. Specifically, even if certain intermediate values or sub-ranges are not explicitly listed in the specification, these values and ranges should still be regarded as being fully disclosed and included in the protection scope of the present invention. Those skilled in the art should understand that any reasonable change or adjustment based on the disclosed numerical ranges, as long as its numerical points or sub-ranges fall within the original disclosed numerical range, should belong to the protection scope of the present invention.

[0033] Example 1

[0034] An anti-corrosion material, the preparation method comprising the following steps:

[0035] (1) The preparation method of A3T2 molecular cage is as follows: Dissolve 530 mg of isophthalaldehyde in 30 mL of acetonitrile to obtain an aldehyde solution; dissolve 400 µL of tris(2-aminoethyl)amine in 5 mL of acetonitrile to obtain an amine solution; inject the amine solution into the aldehyde solution, the reaction temperature is 25 °C, stir for 30 h to carry out an amine-aldehyde condensation reaction. After the reaction, wash with 30 mL of acetonitrile 3 - 5 times, and dry at 40 °C to obtain a white powder, which is A3T2 molecular cage (C 36 N8H 42 ), and the molecular structural formula is as shown in Formula I.

[0036] Formula I.

[0037] (2) Weigh 96 mg of A3T2 molecular cage and 120 mg of sodium tetraphenylborate, dissolve them in 10 mL of a mixed solution of chloroform, acetonitrile and ethanol (the volume ratio of chloroform, acetonitrile and ethanol in the mixed solution is 5:20:3), ultrasonicate for 15 min at 25 °C to fully dissolve them, and then filter using an organic filter membrane to obtain a uniformly dispersed anti-corrosion material of copper complex coated with molecular cage.

[0038] Application Example 1

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

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

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

[0042] Perform electron microscopy scans on the pretreated copper foil and the passivated copper foil respectively. The SEM images are as shown in Figure 1 and Figure 2 It can be seen that the surface of the pretreated copper foil in Figure 1 is smooth, and Figure 2 a thin film is formed on the surface of the passivated copper foil.

[0043] After the pretreated copper foil and the passivated copper foil are respectively immersed in 0.1 M NaOH solution for corrosion for 1 week, electron microscopy scans are performed. The SEM images are as shown in Figure 3 and Figure 4 It can be seen from Figure 3 that obvious oxidation corrosion morphology appears on the surface of the pretreated copper foil, and there are many oxide particles on the surface of the copper foil, and the roughness increases significantly. It can be seen from Figure 4 that after the copper foil passivated with the anti-corrosion material of copper complex coated with molecular cage of the present invention is immersed under the same conditions, its surface morphology is the same as before immersion ( Figure 2There was no obvious change compared with that before, which proved that after the copper complex anti-corrosion material of the present invention was coated on the surface of the copper foil, a composite passivation layer with a multi-level protection structure was formed on the surface of the copper substrate, significantly improving the antioxidant performance of the copper foil and still maintaining excellent surface stability in an alkaline environment.

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

[0045] After the pretreated copper foil and the passivated copper foil of Application Example 1 were respectively immersed in 0.1 M sodium hydroxide solution for corrosion for 1 week, conductivity tests were carried out, and the results are as Figure 6 shown. It can be seen that after the pretreated copper foil was corroded, the conductivity decreased significantly, and after the passivated copper foil of Application Example 1 was corroded, the decrease in conductivity was lower.

[0046] Example 2

[0047] An anti-corrosion material, the preparation method includes the following steps:

[0048] (1) Preparation method of D3T2 molecular cage: Dissolve 530 mg of terephthalaldehyde in 30 mL of dichloromethane to obtain an aldehyde solution; dissolve 400 μL of tris(2-aminoethyl)amine in 5 mL of dichloromethane to obtain an amine solution; inject the amine solution into the aldehyde solution, the reaction temperature is 25 °C, stir for 30 h, carry out an amine-aldehyde condensation reaction. After the reaction is completed, wash with 30 mL of dichloromethane 3 - 5 times, and dry at 40 °C to obtain a light yellow powder, namely D3T2 molecular cage (C 36 N8H 42 ), and the molecular structural formula is as shown in Formula II.

[0049] Formula II.

[0050] (2) Weigh 96 mg of D3T2 molecular cage and 120 mg of sodium tetraphenylborate, dissolve them in a 10 mL mixed solution of chloroform, acetonitrile and ethanol (the volume ratio of chloroform, acetonitrile and ethanol in the mixed solution is 5:20:3), ultrasonicate at 25 °C for 20 min, dissolve them fully, and then filter with an organic filter membrane to obtain a uniformly dispersed copper complex anti-corrosion material coated with molecular cage.

[0051] Application Example 2

[0052] The treatment method is the same as that in Example 1. The prepared double-sided passivated copper foil has no obvious change in its surface morphology compared with that before treatment after being immersed in 0.1 M NaOH solution for corrosion for 7 days.

[0053] Comparative Example 1

[0054] The difference from Example 1 is only that in step (2), 96 mg of A3T2 molecular cage is dissolved in 10 ml of chloroform, and it is ultrasonically dissolved thoroughly, and then the solution is filtered to obtain the copper complex anti-corrosion material for standby.

[0055] Comparative Application Example 1

[0056] The copper complex anti-corrosion material prepared in Comparative Example 1 is used to passivate the copper foil, and the treatment method is the same as that in Application Example 1 to obtain a double-sided passivated copper foil.

[0057] Comparative Example 2

[0058] The preparation method of the anti-corrosion material is as follows: 120 mg of sodium tetraphenylborate is dissolved in a mixed solution of 10 ml of acetonitrile and ethanol (the volume ratio of acetonitrile to ethanol in the mixed solution is 20:3), and it is ultrasonically dissolved thoroughly, and then the solution is filtered to obtain the anti-corrosion material for standby.

[0059] Comparative Application Example 2

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

[0061] Comparative Example 3

[0062] The difference from Example 1 is only that the molecular cage used is RA3T2 molecular cage (C 36 N8H 54 ), and the molecular structural formula is as shown in Formula III.

[0063] [[ID=3D]] Formula III.

[0064] The preparation method of RA3T2 molecular cage is as follows:

[0065] (1) Prepare A3T2 molecular cage, and the preparation method is the same as that in Example 1;

[0066] (2) Dissolve 300 mg of A3T2 molecular cage in a mixed solution of dichloromethane and methanol with a volume ratio of 1:1, add 300 mg of NaBH4, stir and react at room temperature for 15 h, then add 1 mL of water and continue to stir the solution for 9 h, and rotary evaporate to remove the solution. Add 10 ml of water and 10 ml of dichloromethane for extraction, and vacuum dry the product at 40 °C for 24 h to obtain the reduced molecular cage RA3T2.

[0067] Comparative Application Example 3

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

[0069] After immersing the copper foils passivated in Application Examples 1 to 2 and Comparative Application Examples 1 to 3 in a 0.1 M sodium hydroxide solution for corrosion for 1 week, Raman spectroscopy analysis was performed, and the Raman spectra are as follows Figure 7 shown. It can be seen from the figure that no peaks of copper oxide appear in the copper foils passivated in Application Examples 1 to 2, while in the copper foils passivated in Comparative Application Examples 1 to 3, Raman peaks are observed at 150 cm -1 , 290 cm -1 , 335 cm -1 , 628 cm -1 . These peaks are attributed to Cu2O and CuO substances.

[0070] In the above embodiments, the technical solutions of the present invention have been described in detail. However, it should be understood that these specific embodiments are only used to illustrate the technical concept of the present invention, rather than limiting the protection scope of the present invention. Within the basic concept scope of the technical solutions of the present invention, those skilled in the art can make various appropriate modifications and variations, and these modifications and variations should be included within the protection scope of the present invention. It should be particularly noted that each technical feature described in this specification can be combined in any feasible manner without generating technical contradictions. For the sake of brevity, all possible combination methods are not listed one by one in this specification. In addition, any combination can be made between different embodiments of the present invention, 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. An anti-corrosion material, characterized in that, Comprising an organic molecular cage, a hydrophobic compound and an organic solvent, the organic molecular cage being an A3T2 molecular cage or a D3T2 molecular cage, the A3T2 molecular cage being C 36 N8H 42 , the D3T2 molecular cage being C 36 N8H 42 , the mass ratio of the organic molecular cage to the hydrophobic compound being 90 to 100:115 to 130, the hydrophobic compound being one or more of sodium tetraphenylborate, potassium tetraphenylborate, 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, wherein The organic solvent is composed of a mixture of chloroform, acetonitrile, and ethanol with 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: Dissolve terephthalaldehyde powder in acetonitrile to obtain an aldehyde solution; dissolve tris(2-aminoethyl)amine in acetonitrile to obtain an amine solution; inject the amine solution into the aldehyde solution, stir, and carry out an amine-aldehyde condensation reaction. After the reaction is completed, obtain the target product powder, and obtain the A3T2 molecular cage after washing and drying.

6. The preparation method of the D3T2 molecular cage according to the anti-corrosion material described in claim 1 is as follows: Dissolve terephthalaldehyde powder in dichloromethane to obtain an aldehyde solution; dissolve tris(2-aminoethyl)amine in dichloromethane to obtain an amine solution; inject the amine solution into the aldehyde solution, stir, and carry out an amine-aldehyde condensation reaction. After the reaction is completed, obtain the target product powder, and obtain the D3T2 molecular cage after washing and drying.

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

8. The application according to claim 7, wherein The application method is: uniformly coat the anti-corrosion material on the surface of the pretreated copper foil and carry out passivation treatment.

9. The application according to claim 8, wherein The pretreatment includes the following steps: ultrasonically clean the oxide on the surface of the copper foil with an ethanol solution containing 1~2 wt% acetic acid, and then clean the organic matter on the surface with isopropanol; The specific operation steps of the coating are as follows: Drop the anti-corrosion material at one end of the copper foil, use a precision wire bar, apply a constant pressure in a constant temperature environment of 25±2 °C, and pull the wire bar uniformly to ensure that the wire bar is in complete linear contact with the surface of the copper foil, so that the coating liquid spreads evenly on the surface of the copper foil, and let it stand for 10~15 min.

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

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