Preparation method and application of a double-substituted triazole derivative schiff base metal corrosion inhibitor
Patent Information
- Application Number
- CN202410536951.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-30
- Publication Date
- 2026-10-30
- Estimated Expiration
- 2044-04-30
AI Technical Summary
[0004]本发明针对上述现有技术存在的问题，提供一种双取代三唑衍生席夫碱类金属缓蚀剂制备方法，解决了现有技术中氨基单取代的局限性，同时，本发明有效抑制在中性介质体系系统装置中杂菌等各类微生物菌群的生长
[0019]本发明通过对氨基、巯基双取代的三唑进行亚胺化处理，在氨基上引入具有能与金属结合的芳香醛或取代芳香醛，促进了三唑与金属基底的相互作用；同时，三唑上巯基的存在强化了三唑与金属基底的相互作用，提升了三唑类化合物对金属的腐蚀防护性能。
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing a class of high-efficiency metal corrosion inhibitors, and more particularly to a method for preparing and applying a disubstituted triazole-derived Schiff base metal corrosion inhibitor, belonging to the field of fine chemical technology. Background Technology
[0002] Triazole compounds are widely applicable in corrosive media, have a broad temperature range, and are environmentally friendly. They are currently used as important corrosion inhibitors for the protection of various metals. Reportedly, triazole compounds have shown corrosion inhibition effects on iron in high-concentration hydrochloric acid systems at high temperatures that are close to or even exceed those of propanediol under the same conditions. Furthermore, triazoles do not produce toxic gases during acidification operations, fully demonstrating their excellent corrosion protection performance.
[0003] To enhance the protective properties of triazole compounds against metals, researchers in this field have introduced electron-donating groups onto the triazole parent ring to promote the interaction between the triazole compound and the metal substrate. Examples include studies on the corrosion inhibition performance of 3-amino-1,2,4-triazole on copper-nickel alloys in 3% sodium chloride solution. However, current research on the protective properties of triazole compounds against metals is largely limited to introducing new substituents onto amino-substituted triazole rings or modifying the triazole itself. Summary of the Invention
[0004] To address the problems existing in the prior art, this invention provides a method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor, which overcomes the limitations of amino monosubstituted inhibitors in the prior art. At the same time, this invention effectively inhibits the growth of various microbial communities, including miscellaneous bacteria, in neutral media systems.
[0005] A method for preparing a highly efficient metal corrosion inhibitor derived from a disubstituted triazole-based Schiff base includes the following steps:
[0006] Step (1): Prepare alcohol solutions of aromatic aldehydes and disubstituted triazole compounds respectively; the molar ratio of aromatic aldehydes to alcohols is 1:(10-15); the molar ratio of disubstituted triazole compounds to alcohols is 1:(3-5);
[0007] Step (2): Add the disubstituted triazole compound alcohol solution dropwise into the aromatic aldehyde solution;
[0008] Step (3): After the reaction is complete, the obtained material is centrifuged, filtered, and dried to obtain the final product.
[0009] Preferably, in step (1), the aromatic aldehyde is any one of p-hydroxybenzaldehyde, salicylaldehyde, and p-chlorobenzaldehyde.
[0010] Preferably, in step (1), the disubstituted triazole compound is 3-amino-5-mercapto-1,2,4-triazole.
[0011] Preferably, in step (1), the alcohol is anhydrous ethanol.
[0012] Preferably, step (2) further includes a catalyst, wherein the molar ratio of the catalyst to the aromatic aldehyde is 1:(10-20).
[0013] Preferably, in step (2), the catalyst is a weak organic acid, preferably glacial acetic acid.
[0014] Preferably, in step (2), the temperature at which the chemical reaction occurs is 70–100°C, and the reaction time is 4–6 h.
[0015] Preferably, in step (3), when centrifuging and filtering the material, the centrifugal speed is 5000-7000 r / min.
[0016] The finished product is used in corrosion inhibitors at a molar concentration of 20 mM.
[0017] The corrosion inhibitor is used in the protection of metal corrosion, with copper-based substrates being preferred.
[0018] The advantages and effects of this invention are as follows:
[0019] This invention promotes the interaction between triazole and metal substrate by imidizing triazoles with amino and thiol disubstituted groups, introducing aromatic aldehydes or substituted aromatic aldehydes with metal-binding capabilities onto the amino group; at the same time, the presence of thiol groups on the triazole enhances the interaction between the triazole and metal substrate, thereby improving the corrosion protection performance of triazole compounds against metals.
[0020] Furthermore, the introduction of thiol groups, under the action of oxidoreductases in contaminating microorganisms, can form disulfide bonds with thiol groups in protein molecules on the cell membrane of microorganisms, thereby inactivating the microorganisms and effectively inhibiting the growth of various microbial communities, including contaminating microorganisms, in neutral media systems. In addition, the introduction of thiol groups can act as chelating agents, binding to toxic ions such as lead, mercury, and arsenic in the media system through cross-linking, reducing the toxicity of the media system and serving as an effective antidote. The predicted chelation mechanism is shown in the attached figure. Figure 4 As shown.
[0021] This invention provides superior corrosion inhibition performance for triazole compounds. The preparation process and post-treatment are simple, the product yield is high, the reaction conditions are mild and environmentally friendly, and it exhibits excellent corrosion protection for metals. Especially for media systems containing oxides, the redox properties of the nitrogen-nitrogen bonds in the triazole derivatives can slow down the oxidation of copper by the media, reduce corrosion, and enhance the corrosion inhibition performance of the corrosion inhibitor. This invention is worthy of widespread application in the industry.
[0022] This invention eliminates the need for a catalyst, reducing the amount of raw materials used or subsequent processing steps, thus lowering costs. This is primarily because, without a catalyst, the amino group in the disubstituted triazole can normally attack the carbonyl carbon, balancing the attack of hydrogen ions on oxygen to form a tetrahedral structure, ultimately resulting in a dehydration reaction and iminolation. However, in the presence of an acidic catalyst, its protons can rapidly attack the carbonyl oxygen of the aromatic aldehyde, promoting the formation of a carbocation on the carbonyl group, or attack the hydroxyl group in the intermediate to form a hydrated ion, further promoting iminolation. Therefore, a small amount of catalyst can be added in the experiment to accelerate the conversion of the raw materials. Attached Figure Description
[0023] Figure 1 The diagram shown is a schematic of the film-forming contact angle of the corrosion inhibitor of the present invention;
[0024] Figure 2 The figure shown is a schematic diagram of the polarization curve of the corrosion inhibitor of the present invention;
[0025] Figure 3 The image shows the impedance spectrum of the corrosion inhibitor of the present invention.
[0026] Figure 4 The diagram shows the chelation mechanism between the corrosion inhibitor of the present invention and mercury. Detailed Implementation
[0027] To illustrate the technical content, objectives, and effects of this invention in detail, detailed descriptions are provided in conjunction with embodiments and accompanying drawings. In the specific embodiments, the process conditions and reagents used are merely illustrative and should not be considered as limitations on the technical solution of this invention. The disubstituted triazole compounds selected in this invention all contain both thiol and amino-substituted triazole compounds, and the terms "above" and "below" in this invention include the stated number.
[0028] Comparative Example 1
[0029] Weigh 0.03 mol of 4-amino-1,2,4-triazole and dissolve it in 8 mL of anhydrous ethanol. Slowly add the aminotriazole solution to an alcoholic solution of p-hydroxybenzaldehyde, which was prepared by dissolving 0.03 mol of p-hydroxybenzaldehyde in 20 mL of anhydrous ethanol. Maintain the temperature at 90 °C during the addition process, reflux the reaction for 6 h, terminate the reaction, allow it to stand until room temperature, centrifuge and filter, and place it in a vacuum drying oven to remove moisture to obtain the final product (Compound 1).
[0030]
[0031] At room temperature, the product obtained above was self-assembled onto a copper sheet at a concentration of 20 mM for 6 hours. Its corrosion inhibition performance was evaluated by placing it in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 88.2%.
[0032] Comparative Example 2
[0033] Compared to Control Example 1, the substitution site of the hydroxyl group on the main ring of the aromatic aldehyde was changed. 0.03 mol of 4-amino-1,2,4-triazole was weighed and dissolved in 8 mL of anhydrous ethanol. The aminotriazole solution was slowly added dropwise to an alcoholic solution of salicylaldehyde, which was prepared by dissolving 0.03 mol of p-methylbenzaldehyde in 20 mL of anhydrous ethanol. The temperature was maintained at 90°C during the addition, and the reaction was refluxed for 6 hours. The reaction was then terminated, allowed to stand until room temperature, centrifuged and filtered, and the product was placed in a vacuum drying oven to remove moisture, yielding the final product (Compound 2).
[0034]
[0035] At room temperature, the product obtained above was self-assembled onto a copper sheet at a concentration of 20 mM for 6 hours. Its corrosion inhibition performance was evaluated by placing it in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 89.8%. Specific Implementation Example 1
[0037] Compared to Control Example 1, the aminotriazole was replaced with a disubstituted triazole compound. 0.03 mol of 3-amino-5-mercapto-1,2,4-triazole was weighed and dissolved in 8 mL of anhydrous ethanol. The disubstituted triazole solution was slowly added dropwise to the solution of p-hydroxybenzaldehyde.
[0038] 0.03 mol of p-hydroxybenzaldehyde was dissolved in 20 mL of anhydrous ethanol. The temperature was maintained at 90 °C during the dropwise addition, and the reaction was refluxed for 6 h. The reaction was then terminated, allowed to stand until room temperature, centrifuged and filtered, and placed in a vacuum drying oven to remove moisture to obtain the final product (Compound 3).
[0039]
[0040] At room temperature, the product obtained above was self-assembled onto a copper sheet at a concentration of 20 mM over a period of 6 hours. Its corrosion inhibition performance was then evaluated in a 3.5 wt% NaCl solution, with a maximum inhibition efficiency of 90%. The corrosion inhibition efficiency of the obtained inhibitor was higher than that of the corrosion inhibitor without mercapto substitution. Specific Implementation Example 2
[0042] 2. Replace the aminotriazole with a disubstituted triazole compound. Weigh 0.03 mol of 3-amino-5-mercapto-1,2,4-triazole and dissolve it in 8 mL of anhydrous ethanol. Slowly add the disubstituted triazole alcohol solution to an alcoholic solution of salicylaldehyde, which was prepared by dissolving 0.03 mol of salicylaldehyde in 20 mL of anhydrous ethanol. Maintain the temperature at 90 °C during the addition process, reflux the reaction for 6 h, terminate the reaction, allow it to stand until room temperature, centrifuge and filter, and place it in a vacuum drying oven to remove moisture to obtain the final product (Compound 4).
[0043]
[0044] At room temperature, the product obtained above was self-assembled onto a copper sheet at a concentration of 20 mM for 6 hours. Its corrosion inhibition performance was evaluated by placing it in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 94.4%. Specific Implementation Example 3
[0046] Based on Specific Examples 1 and Specific Examples 2, the corrosion inhibition performance was evaluated by changing the type of aromatic aldehyde substituent. 0.03 mol of 3-amino-5-mercapto-1,2,4-triazole was weighed and dissolved in 8 mL of anhydrous ethanol. A disubstituted triazole alcohol solution was slowly added dropwise to an alcoholic solution of p-chlorobenzaldehyde, which was prepared by dissolving 0.03 mol of p-chlorobenzaldehyde in 20 mL of anhydrous ethanol. The temperature was maintained at 90°C during the addition process, and the reaction was refluxed for 6 hours. The reaction was then terminated, allowed to stand until room temperature, centrifuged and filtered, and the product was placed in a vacuum drying oven to remove moisture, obtaining the final product (Compound 5).
[0047]
[0048] At room temperature, the product obtained above was self-assembled onto a copper sheet at a concentration of 20 mM for 6 hours. Its corrosion inhibition performance was evaluated by placing it in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 94.5%.
[0049] The changes in substituents in aromatic aldehydes still demonstrate the excellent corrosion inhibition properties of this type of Schiff base. Specific Implementation Example 4
[0051] Weigh 0.03 mol of 3-amino-5-mercapto-1,2,4-triazole and dissolve it in 6 mL of anhydrous ethanol (the molar ratio of the prepared disubstituted triazole compound to the alcohol is 1:3). Slowly add the disubstituted triazole alcohol solution to an alcoholic solution of p-hydroxybenzaldehyde, which was prepared by dissolving 0.03 mol of p-hydroxybenzaldehyde in 17 mL of anhydrous ethanol (the molar ratio of the prepared aromatic aldehyde to the alcohol is approximately 1:10). Maintain the temperature at 70 °C during the addition process and reflux for 6 h. Terminate the reaction, allow it to stand until room temperature, centrifuge and filter, and place it in a vacuum drying oven to remove moisture to obtain the final product.
[0052] At room temperature, the above-obtained products were self-assembled onto copper sheets at a concentration of 20 mM for 6 hours. The corrosion inhibition performance was then evaluated by placing them in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 90.1%. Specific Implementation Example 5
[0054] Weigh 0.03 mol of 3-amino-5-mercapto-1,2,4-triazole and dissolve it in 10 mL of anhydrous ethanol (the molar ratio of the disubstituted triazole compound to the alcohol is 1:5). Slowly add the disubstituted triazole alcohol solution to an alcoholic solution of p-hydroxybenzaldehyde, which is prepared by dissolving 0.03 mol of p-hydroxybenzaldehyde in 25 mL of anhydrous ethanol (the molar ratio of the aromatic aldehyde to the alcohol is approximately 1:15). Maintain the temperature at 100 °C and reflux for 4 h during the addition process. Terminate the reaction, allow it to stand until room temperature, centrifuge and filter, and place it in a vacuum drying oven to remove moisture to obtain the final product.
[0055] At room temperature, the above-obtained products were self-assembled onto copper sheets at a concentration of 20 mM for 6 hours. The corrosion inhibition performance was then evaluated by placing them in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 90.5%. Specific Implementation Example 6
[0057] Weigh 0.03 mol of 3-amino-5-mercapto-1,2,4-triazole and dissolve it in 8 mL of anhydrous ethanol. Slowly add the disubstituted triazole alcohol solution to the alcoholic solution of p-hydroxybenzaldehyde, which was prepared by dissolving 0.03 mol of p-hydroxybenzaldehyde in 20 mL of anhydrous ethanol. Glacial acetic acid was used as a catalyst. The temperature was maintained at 90 °C during the addition process, and the reaction was refluxed for 4 h. The reaction was then terminated, allowed to stand until room temperature, centrifuged and filtered, and the product was placed in a vacuum drying oven to remove moisture and obtain the final product.
[0058] At room temperature, the above-obtained products were self-assembled onto copper sheets at a concentration of 20 mM for 6 hours. The corrosion inhibition performance was then evaluated by placing them in a 3.5 wt% NaCl solution, and the maximum corrosion inhibition efficiency was 90.2%.
[0059] It is understood that those skilled in the art can make various corresponding changes and modifications based on the technical concept of this invention, and all such changes and modifications should fall within the protection scope of the claims of this invention. Appendix 1 shows the impedance test results parameters of the high-efficiency corrosion inhibitors involved in the embodiments.
[0060]
Claims
1. A method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor, characterized in that, Includes the following steps: Step (1): Prepare alcohol solutions of aromatic aldehydes and disubstituted triazole compounds respectively; the molar ratio of aromatic aldehydes to alcohols is 1:(10-15); the molar ratio of disubstituted triazole compounds to alcohols is 1:(3-5). Step (2): Add the alcoholic solution of the disubstituted triazole compound dropwise into the aromatic aldehyde solution; Step (3): After the reaction is complete, the obtained material is centrifuged, filtered, and dried to obtain the final product; In step (1), the aromatic aldehyde is any one of p-hydroxybenzaldehyde, salicylaldehyde, and p-chlorobenzaldehyde; The disubstituted triazole compound is 3-amino-5-mercapto-1,2,4-triazole.
2. The method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 1, characterized in that, In step (1), the alcohol is anhydrous ethanol.
3. The method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 1, characterized in that, Step (2) also includes a catalyst, with a molar ratio of catalyst to aromatic aldehyde of 1:(10-20).
4. The method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 3, characterized in that, In step (2), the catalyst is a weak organic acid.
5. The method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 4, characterized in that, In step (2), the catalyst is glacial acetic acid.
6. The method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 1, characterized in that, In step (2), the temperature at which the chemical reaction occurs is 70–100 °C, and the reaction time is 4–6 h.
7. The method for preparing a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 1, characterized in that, In step (3), when centrifuging and filtering the material, the centrifugal speed is 5000-7000 r / min.
8. The application of a disubstituted triazole-derived Schiff base metal corrosion inhibitor, characterized in that, The bis-substituted triazole-derived Schiff base metal corrosion inhibitor prepared by any one of claims 1-7 is applied to metal corrosion protection, wherein the molar concentration of the corrosion inhibitor during application is 20 mM.
9. The application of a disubstituted triazole-derived Schiff base metal corrosion inhibitor according to claim 8, characterized in that, The metal is a copper-based substrate.