Corrosion inhibitor based on metal organic framework as well as preparation method and application of corrosion inhibitor

Abstract

The invention discloses a corrosion inhibitor based on a metal organic framework and a preparation method and application thereof, and belongs to the technical field of metal material corrosion inhibitors. The corrosion inhibitor comprises the following components in parts by weight: 50-60 parts of imidazole derivative / Zn < 2 + > MOFs; 40-60 parts by weight of small molecular alcohol; 20-45 parts by weight of a strong polar organic solvent; the imidazole derivative comprises an alkyl imidazole derivative. MOFs functional materials based on different organic ligands are developed, and corrosion of copper in a neutral medium is inhibited through the synergistic effect of imidazole rings and metal ions in MOFs; the MOFs corrosion inhibitor has a remarkable corrosion inhibition effect.

Description

Technical Field

[0001] The invention belongs to the technical field of metal material corrosion inhibitors, and in particular relates to a metal organic framework-based corrosion inhibitor and a preparation method and application thereof. Background Art

[0002] In the application process of metal materials, corrosion has always been one of the key factors affecting material performance and service life. Especially for copper and its alloys, corrosion protection is particularly important due to their wide application in various environments, such as electrical, construction, marine engineering and other fields.

[0003] Metal-organic frameworks (MOFs) are a new type of crystalline porous materials that have attracted much attention due to their unique structure and properties. MOFs are composed of metal ion clusters or metal oxide clusters connected to organic linkers through coordination bonds, forming a highly ordered and regular porous network structure. MOFs have strong structural stability and most of them are highly hydrophobic, which makes them ideal candidate materials for the preparation of efficient corrosion inhibitors.

[0004] In the prior art, for example, publication number CN 110129803 A discloses a copper corrosion inhibitor based on metal organic framework material MOFs and a preparation method thereof, wherein the technical scheme is: using aminobenzimidazole / Zn 2+ MOFs is the key main material for copper corrosion inhibitors. 2+ The strong hydrophobicity and stable structure of MOFs adsorption groups can play a good role in inhibiting the corrosion of copper or copper alloy materials. 2+ MOFs have a relatively simple structure and lack complex multi-ring or multi-metal node connections. Their stability in harsh environments such as high temperature and strong acid and alkali may be poor, which causes the corrosion inhibitor to easily degrade during use and lose its protective effect. Summary of the invention

[0005] Purpose of the invention: In order to solve the above problems, the present invention provides a corrosion inhibitor based on a metal organic framework and a preparation method and application thereof.

[0006] Technical solution: Corrosion inhibitors based on metal organic frameworks, including:

[0007] Imidazole derivatives / Zn 2+ MOFs, 50-60 parts by weight;

[0008] Small molecule alcohol, 40-60 parts by weight;

[0009] Strong polar organic solvent, 20-45 parts by weight;

[0010] The imidazole derivative / Zn 2+The structural formula of MOFs is as follows:

[0011]

[0012] In the formula, R is an alkyl group.

[0013] In further embodiments, the alkyl group is ethyl, butyl, or undecyl.

[0014] In another technical solution, a method for preparing a metal organic framework-based corrosion inhibitor is provided, which is used to prepare the metal organic framework-based corrosion inhibitor as described above, and the preparation method comprises the following steps:

[0015] Step 1, dissolving the zinc compound and the imidazole derivative in an organic solvent according to a predetermined ratio to obtain a mixture; wherein the predetermined ratio is: the molar ratio of the zinc ion in the zinc compound to the imidazole derivative is 1:1-4;

[0016] Step 2, after subjecting the mixture to ultrasonic vibration, heating the mixture for reaction; wherein the heating conditions are: first, keeping the mixture at 60-80° C. for reaction for 30 minutes to 3 hours; then continuing to increase the temperature, keeping the mixture at 100-150° C. for reaction for 12 to 48 hours;

[0017] Step 3: After the heating reaction is completed, cool to room temperature to obtain a solid product; wash, centrifuge and dry the solid product in sequence to obtain an imidazole derivative / Zn 2+ MOFs;

[0018] Step 4: the imidazole derivative / Zn 2+ The MOFs, small molecule alcohol and strong polar organic solvent are stirred and mixed to obtain a corrosion inhibitor.

[0019] In a further embodiment, the zinc compound in step 1 is one of zinc sulfate, zinc carbonate, zinc nitrate, or zinc nitrate tetrahydrate.

[0020] In a further embodiment, the organic solvent in step 1 is one of N-N dimethylformamide, formamide, or N-N dimethylacetamide.

[0021] In a further embodiment, the amount of the organic solvent used in step 1 is 500-1200 mL.

[0022] In a further embodiment, the small molecule alcohol in step 4 is one of methanol, ethanol, or isopropanol.

[0023] In a further embodiment, the highly polar organic solvent in step 4 is one of N,N-dimethylformamide, formamide, or dimethyl sulfoxide.

[0024] In another technical solution, there is provided the use of the metal organic framework-based corrosion inhibitor as described above in a copper corrosion inhibitor, characterized in that the copper includes single copper and copper alloy materials.

[0025] The present invention is used to prepare imidazole derivatives / Zn 2+ When synthesizing MOFs, a solvent thermal reaction is used. During the heating process, the heating temperature should rise steadily and evenly. The heating should be divided into two stages, and the temperature and time of each stage should be controlled so that MOFs can be successfully synthesized. In the first stage, the reaction is kept at 60-80°C for 0.5-3 hours to allow the two reactants to react fully. In the second stage, the temperature is continued to rise to 100-150°C for 12-48 hours to provide temperature conditions for the growth of MOFs. This provides a suitable temperature condition for the reaction as a whole, which is conducive to the growth of MOFs.

[0026] The imidazole derivative / Zn 2+ The mass ratio of MOFs, small molecule alcohol and strong polar organic solvent is set to (50-60): (40-60): (20-45); the above mass ratio makes the imidazole derivative / Zn in the corrosion inhibitor system 2+ The MOFs are completely dissolved, and the corrosion inhibition effect is optimal. The small molecular alcohol in the present invention is used to promote the fluidity of MOFs containing imidazole derivatives / Zn2+; the strong polar organic solvent has good solubility and can dissolve the synthesized MOFs solid; the imidazole derivatives / Zn 2+ The synergistic effect of MOFs, small molecule alcohols and highly polar organic solvents enables the corresponding corrosion inhibitor as a whole to effectively inhibit the corrosion of copper or copper alloy materials.

[0027] Beneficial effects:

[0028] (1) The present invention develops MOFs-based functional materials based on different organic ligands, and inhibits the corrosion of metallic copper in neutral media through the synergistic effect of imidazole rings and metal ions in MOFs; MOFs-based corrosion inhibitors have significant corrosion inhibition effects.

[0029] (2) The copper corrosion inhibitor of the present invention is imidazole derivative / Zn 2+ MOFs is the main component, which can effectively inhibit the corrosion of copper; and the dosage of the corrosion inhibitor is extremely low (can be as low as below 30 mg / L), and the corrosion inhibition effect is significant, while also being green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a flow chart of the preparation method of the present invention;

[0031] Figure 2 are different imidazole derivatives / Zn 2+SEM image of MOFs.

[0032] Figure 3 are different imidazole derivatives / Zn 2+ Thermogravimetric images of MOFs. DETAILED DESCRIPTION

[0033] In the prior art, aminobenzimidazole and zinc compound are used as raw materials to prepare metal organic framework aminobenzimidazole / Zn 2+ MOFs and aminobenzimidazole / Zn 2+ MOFs are applied to copper corrosion inhibitors to inhibit the corrosion of copper or copper alloys. 2+ MOFs are composed of only two benzimidazole rings and have a simple structure, which limits their adaptability and functional diversity in different environments. Since there are only two benzimidazole rings, the number of coordination sites they can provide is relatively small, which affects their coverage efficiency and protective effect when used as copper corrosion inhibitors.

[0034] Compared with the prior art, the imidazole derivative / Zn 2+ MOFs structure, stable network structure formed by zinc ions, imidazole derivatives / Zn 2+ MOFs have higher thermodynamic stability when used as copper corrosion inhibitors (e.g. Figure 3 It is not easy to decompose and fail under high temperature or strong acid and alkali conditions, and still maintains a good corrosion inhibition effect. Moreover, compared with the prior art, the present invention can provide more coordination sites, can better wrap the copper surface, form a denser protective layer, and improve its coverage efficiency and protective effect when used as a copper corrosion inhibitor.

[0035] The following specific examples illustrate the preparation method of the present invention and the imidazole derivative / Zn 2+ MOFs as copper corrosion inhibitors:

[0036] Example 1

[0037] 56 g of zinc nitrate, 60 g of 2-ethylimidazole and 800 mL of N,N-dimethylformamide were mixed and ultrasonically vibrated for 30 minutes at room temperature to mix evenly; the evenly mixed mixture was transferred to a closed reactor for a heated solvent thermal reaction, and the reaction temperature was maintained for 1 hour after the reaction temperature reached 80°C; the temperature was continued to be raised to 140°C and the temperature was maintained for 24 hours; after the heating reaction was completed, the mixture was cooled to room temperature to obtain a solid product; the solid product was washed, centrifuged and dried in sequence to obtain 2-ethylimidazole / Zn 2+ MOFs.

[0038] Add 50 g of the 2-ethylimidazole / Zn prepared above into a beaker. 2+MOFs, 40 g of isopropanol, and 20 g of N,N-dimethylformamide to obtain 110 g of copper corrosion inhibitor.

[0039] Corrosion inhibition performance evaluation:

[0040] At 25°C, 0.5M NaCl solution, the weight loss hanging plate method was used to evaluate the corrosion inhibition performance of the copper corrosion inhibitor in this example on red copper, and the weight loss hanging plate time was 72 hours. Table 1 shows the comparative evaluation results of the corrosion inhibitor in this example and commercially available mercaptobenzothiazole.

[0041] Table 1

[0042] Addition amount (mg / L) Corrosion rate (mm / a) Corrosion inhibition efficiency (%) blank 0 0.0512 / Corrosion inhibitor of the present invention 15 0.00458 91.05 Mercaptobenzothiazole 15 0.00942 81.60

[0043] It can be seen from the test data in Table 1 that in the evaluation system, the corrosion inhibitor of this embodiment has a significant inhibitory effect on the corrosion of copper, and the corrosion inhibition performance is also better than that of commercially available mercaptobenzothiazole products.

[0044] Example 2

[0045] 50 g of zinc sulfate, 100 g of 2-butylimidazole and 700 mL of N,N-dimethylformamide were mixed and ultrasonically vibrated for 30 minutes at room temperature to mix evenly; the evenly mixed mixture was transferred to a closed reactor for a heated solvent thermal reaction, and when the reaction temperature reached 60°C, the temperature was maintained for 0.5 hours; the temperature was continued to be raised to 120°C and the temperature was maintained for 18 hours; after the heating reaction was completed, the mixture was cooled to room temperature to obtain a solid product; the solid product was washed, centrifuged and dried in sequence to obtain 2-butylimidazole / Zn 2+ MOFs.

[0046] Add 50 g of the 2-butylimidazole / Zn prepared above into a beaker. 2+ MOFs, 50 g methanol, 30 g formamide, and 130 g copper corrosion inhibitor were obtained.

[0047] Corrosion inhibition performance evaluation:

[0048] The corrosion inhibition performance of the copper corrosion inhibitor of this embodiment on red copper was evaluated by weight loss hanging plate method at 50°C and 0.3M NaCl solution, and the weight loss hanging plate time was 72 hours. Table 2 shows the comparative evaluation results of the corrosion inhibitor of this embodiment and commercially available benzotriazole.

[0049] Table 2

[0050] Addition amount (mg / L) Corrosion rate (mm / a) Corrosion inhibition efficiency (%) blank 0 0.0458 / Corrosion inhibitor of the present invention 15 0.00554 87.90 Benzotriazole 15 0.00835 81.77

[0051] It can be seen from the test data in Table 2 that in the evaluation system, the corrosion inhibitor of this embodiment has a significant corrosion inhibition effect on red copper, and the corrosion inhibition performance is also better than that of commercially available benzotriazole products.

[0052] Example 3

[0053] 56 g of zinc nitrate, 65 g of 2-undecyl imidazole and 1000 mL of N, N-dimethylformamide were mixed and ultrasonically vibrated for 30 minutes at room temperature to mix evenly; the evenly mixed mixture was transferred to a closed reactor for a heated solvent thermal reaction, and the reaction temperature was maintained at 80°C for 2 hours; the temperature was further raised to 150°C and the temperature was maintained for 36 hours; after the heating reaction was completed, the mixture was cooled to room temperature to obtain a solid product; the solid product was washed, centrifuged and dried in sequence to obtain 2-undecyl imidazole / Zn 2+ MOFs.

[0054] Add 55 g of the 2-undecyl imidazole / Zn prepared above into a beaker. 2+ MOFs, 45 g ethanol, 40 g formamide, and 140 g copper corrosion inhibitor were obtained.

[0055] Corrosion inhibition performance evaluation:

[0056] The corrosion inhibition performance of the copper corrosion inhibitor of this embodiment on red copper was evaluated by weight loss hanging plate method at 60°C and 0.2M NaCl solution, and the weight loss hanging plate time was 72 hours. Table 3 shows the comparative evaluation results of the corrosion inhibitor of this embodiment and commercially available mercaptobenzothiazole.

[0057] Table 3

[0058] Addition amount (mg / L) Corrosion rate (mm / a) Corrosion inhibition efficiency (%) blank 0 0.0503 / Corrosion inhibitor of the present invention 15 0.00716 85.77 Mercaptobenzothiazole 15 0.00983 80.46

[0059] It can be seen from the test data in Table 3 that in the evaluation system, the corrosion inhibitor of this embodiment has a significant corrosion inhibition effect on red copper, and the corrosion inhibition performance is also better than that of commercially available mercaptobenzothiazole products.

[0060] In addition to the highly polar organic solvents N,N-dimethylformamide and N,N-dimethylacetamide used in the solvothermal reaction in the above embodiments, methanol can also be used as a solvent as long as it can dissolve the reactants, has a high boiling point, does not decompose within a given range, and does not participate in the reaction.

[0061] like Figure 2 As shown, the imidazole derivative / Zn prepared in the above embodiment 2+ SEM images of MOFs;

[0062] (a) is 2-ethylimidazole / Zn 2+ MOFs;

[0063] (b) is 2-butylimidazole / Zn 2+ MOFs;

[0064] (c) is 2-undecyl imidazole / Zn 2+MOFs;

[0065] It can be seen from the SEM images that the morphology of MOFs with different organic ligands is angular blocks, which are rhombic dodecahedrons with regular and orderly shapes, relatively complete, and stacking phenomena.

[0066] like Figure 3 As shown, the imidazole derivative / Zn prepared in the above embodiment 2+ Comparison of thermogravimetric images of MOFs and control group; the control group is aminobenzimidazole / Zn 2+ MOFs.

Claims

1. A corrosion inhibitor based on a metal organic framework, characterized in that: include: Imidazole derivatives / Zn 2+ MOFs, 50-60 parts by weight; Small molecule alcohol, 40-60 parts by weight; Strong polar organic solvent, 20-45 parts by weight; The imidazole derivative / Zn 2+ The structural formula of MOFs is as follows: In the formula, R is an alkyl group.

2. The metal organic framework-based corrosion inhibitor according to claim 1, characterized in that The alkyl group is ethyl, butyl, or undecyl.

3. A method for preparing a metal organic framework-based corrosion inhibitor, for preparing the metal organic framework-based corrosion inhibitor as claimed in claim 1 or 2, characterized in that: The preparation method comprises the following steps: Step 1, dissolving the zinc compound and the imidazole derivative in an organic solvent according to a predetermined ratio to obtain a mixture; wherein the predetermined ratio is: the molar ratio of the zinc ion in the zinc compound to the imidazole derivative is 1:1-4; Step 2, after subjecting the mixture to ultrasonic vibration, heating the mixture for reaction; wherein the heating conditions are: first, keeping the mixture at 60-80° C. for reaction for 30 minutes to 3 hours; then continuing to increase the temperature, keeping the mixture at 100-150° C. for reaction for 12 to 48 hours; Step 3: After the heating reaction is completed, cool to room temperature to obtain a solid product; wash, centrifuge and dry the solid product in sequence to obtain an imidazole derivative / Zn 2+ MOFs; Step 4: the imidazole derivative / Zn 2+ The MOFs, small molecule alcohol and strong polar organic solvent are stirred and mixed to obtain a corrosion inhibitor.

4. The method for preparing a metal organic framework-based corrosion inhibitor according to claim 3, characterized in that: The zinc compound in step 1 is one of zinc sulfate, zinc carbonate, zinc nitrate, or zinc nitrate tetrahydrate.

5. The method for preparing a metal organic framework-based corrosion inhibitor according to claim 3, characterized in that: The organic solvent in step 1 is one of N-N-dimethylformamide, formamide, or N-N-dimethylacetamide.

6. The method for preparing a metal organic framework-based corrosion inhibitor according to claim 3, characterized in that: The amount of the organic solvent used in the step 1 is 500-1200 mL.

7. The method for preparing a metal organic framework-based corrosion inhibitor according to claim 3, characterized in that: The small molecule alcohol in step 4 is one of methanol, ethanol, or isopropanol.

8. The method for preparing a metal organic framework-based corrosion inhibitor according to claim 3, characterized in that: The highly polar organic solvent in step 4 is one of N,N-dimethylformamide, formamide, or dimethyl sulfoxide.

9. The use of the metal organic framework-based corrosion inhibitor in a copper corrosion inhibitor according to claim 1 or 2, characterized in that: The copper includes copper alone and copper alloy materials.

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