A highly corrosion-resistant BTA composite special copper corrosion inhibitor and its preparation method

Abstract

This application relates to the technical field of metal material corrosion and protection, and specifically discloses a highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor and a preparation method thereof. A highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor comprises the following raw materials in parts by weight: 10-25 parts of benzotriazole, 15-28 parts of sodium hydroxide, 3-5 parts of an auxiliary agent, 2-5 parts of polyaspartic acid, 3-8 parts of sodium tungstate, 5-8 parts of zinc gluconate, 1-3 parts of adipic dihydrazide, and 60-70 parts of water. The highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor of this application forms a dense and stable protective film on the surface of metallic copper through the synergistic compounding of polyaspartic acid, sodium tungstate, and zinc gluconate, reduces the corrosion of metallic copper by corrosive media, and improves the anti-corrosion protection efficiency of the corrosion inhibitor for metallic copper.

Description

Technical Field

[0001] This application relates to the technical field of metal material corrosion and protection. More specifically, it relates to a highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor and a preparation method thereof. Background Art

[0002] Copper has excellent stability, strength, ductility, electrical conductivity and machining properties, and is widely used in the fields of electric power, electronics, energy and petrochemical, machinery and metallurgy, emerging industries, etc. It ranks second only to aluminum in the consumption of non-ferrous metal materials in China.

[0003] Copper metal has better corrosion resistance than many metals. Therefore, copper products generally have a long service life. However, copper products are not permanently corrosion-resistant. As the use time prolongs, when copper metal is exposed to air and moisture for a long time, water molecules and oxygen will have a greater erosion effect on copper metal, affecting the service life of copper, and thus bringing serious safety hazards to the use and processing of copper products. Summary of the Invention

[0004] In order to improve the corrosion resistance of metallic copper, this application provides a highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor and a preparation method thereof.

[0005] In the first aspect, this application provides a highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor, adopting the following technical solution:

[0006] A highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor, comprising the following raw materials in parts by weight: 10 - 25 parts of benzotriazole, 15 - 28 parts of sodium hydroxide, 3 - 5 parts of auxiliary agent, 2 - 5 parts of polyaspartic acid, 3 - 8 parts of sodium tungstate, 5 - 8 parts of zinc gluconate, 1 - 3 parts of adipic dihydrazide, and 60 - 70 parts of water.

[0007] By adopting the above technical solution, benzotriazole is used to provide corrosion protection for metallic copper. The negative ions of benzotriazole and cuprous ions form a stable and insoluble complex on the surface of metallic copper, and the complex is firmly adsorbed on the surface of metallic copper, thereby forming a stable and dense protective film on the surface of metallic copper, thus achieving the corrosion protection of metallic copper. Adipic dihydrazide can form a stable complex with metallic copper, and at the same time has multiple bioactive groups and has a certain hydrogen bond action with other compounds, thereby playing a corrosion inhibition effect and a role in sterilization and bacteriostasis. The gluconate anion and zinc ion both have a certain corrosion inhibition effect on metallic copper. Zinc gluconate can inhibit the oxygen reduction reaction of metallic copper in corrosive water and prevent oxygen from diffusing to the metal surface, thereby playing a corrosion protection role for metallic copper, and thus improving the corrosion resistance of metallic copper.

[0008] The carboxyl functional groups of polyaspartic acid can be adsorbed on the surface of metallic copper to form an organic adsorption film on the metal surface, which can hinder the diffusion of water molecules, dissolved oxygen, and corrosion ions to the metal, inhibiting the further oxidation of copper caused by hydration or the erosion of corrosion ions. Thus, it plays a corrosion inhibition role on the surface of metallic copper and improves the corrosion resistance of metallic copper. Sodium tungstate is an inorganic corrosion inhibitor that can form a passivation film on the metal surface through its own oxidizing property, thereby playing an anti-corrosion protection role for metallic copper. Through the synergistic anti-corrosion protection effect of polyaspartic acid and sodium tungstate on metallic copper, the protection of metallic copper is strengthened in both organic and inorganic ways, further improving the corrosion resistance of copper.

[0009] Preferably, the corrosion inhibitor raw material further includes 3 - 5 parts of sodium lignosulfonate.

[0010] By adopting the above technical solution, sodium lignosulfonate, as a cathodic corrosion inhibitor, can increase the ion concentration of the corrosion inhibitor and improve the corrosion inhibition performance of the corrosion inhibitor. The phenolic hydroxyl groups, alcoholic hydroxyl groups, and oxygen atoms on the sodium lignosulfonate molecule all have unshared electron pairs, which can form stable chelates with metal ions, prompting sodium lignosulfonate to firmly bind to the surface of metallic copper to form an insoluble protective film, inhibiting the cathodic process of metallic copper corrosion. And polyaspartic acid belongs to anodic corrosion inhibitor, which can be compounded with sodium lignosulfonate to further improve the corrosion resistance of the metal.

[0011] Preferably, the corrosion inhibitor raw material further includes 0.5 - 2 parts of lysine.

[0012] By adopting the above technical solution, the amino group of lysine can graft with the amide group of polyaspartic acid, increasing the number of lone electrons on the formed polymer, enabling it to form coordination bonds with more empty orbitals of metallic copper atoms, and making it easier to form a protective film on the metal surface, further enhancing the protective effect of the corrosion inhibitor on metallic copper.

[0013] Preferably, the corrosion inhibitor raw material further includes 1 - 3 parts of chitosan.

[0014] By adopting the above technical solution, chitosan has excellent biodegradability. Cationic chitosan can form a polyelectrolyte complex with negatively charged sodium lignosulfonate through electrostatic complexation. The molecular chains in sodium lignosulfonate crosslink with the amino groups in chitosan to form a sodium lignosulfonate-chitosan complex with a certain porous gel structure, which can have better chemical adsorption and physical adsorption effects on metallic copper ions, improving the adsorption efficiency of the corrosion inhibitor for copper ions, and thus promoting the corrosion inhibitor to better play an anti-corrosion protection role on metallic copper.

[0015] Preferably, the auxiliary agent is isopropanol.

[0016] By adopting the above technical solution, adding isopropanol to the corrosion inhibitor can play the roles of corrosion inhibition and dispersibility. On the one hand, it promotes the uniform dispersion of each component in the corrosion inhibitor on the surface of metallic copper, improves the storage stability of the corrosion inhibitor, and thus better plays the role of anti-corrosion protection for metallic copper. On the other hand, the structure of isopropanol has both a lipophilic group and a hydrophilic group. The hydrophilic group side adsorbs on the surface of metallic copper, while the hydrophobic group side is far away from metallic copper, forming a protective film on the surface of metallic copper, thereby slowing down the corrosion efficiency of metallic copper.

[0017] Secondly, the present application provides a preparation method of a highly corrosion-resistant BTA composite special copper corrosion inhibitor, adopting the following technical solution:

[0018] A preparation method of a highly corrosion-resistant BTA composite special copper corrosion inhibitor includes the following specific steps:

[0019] Mix polyaspartic acid, sodium tungstate, adipic dihydrazide, water and an auxiliary agent and heat them for reaction to form a mixed solution A. Then add zinc gluconate to the mixed solution A and heat it for reaction to form a mixed solution B. Finally, add benzotriazole and sodium hydroxide to the mixed solution B for reaction, filter, and cool down to obtain a highly corrosion-resistant BTA composite special copper corrosion inhibitor.

[0020] Preferably, the reaction temperature of the mixed solution A is 70 - 85 °C, and the reaction temperature of the mixed solution B is 100 - 110 °C.

[0021] By adopting the above technical solution, the prepared copper corrosion inhibitor can firmly adsorb on the surface of metallic copper, thereby forming a protective film on metallic copper. Under the synergistic cooperation of each component, the anti-corrosion protection effect of the corrosion inhibitor on metallic copper is further improved.

[0022] Preferably, mix water, polyaspartic acid and lysine, heat them in an oil bath to 110 - 120 °C for reaction for 1 - 2 h, and then dry to obtain a lysine-polyaspartic acid complex.

[0023] By adopting the above technical solution, at 110 - 120 °C, lysine and polyaspartic acid undergo a thermal polycondensation reaction to form a protective film on the surface of metallic copper, slow down the corrosion efficiency of metallic copper, and improve the corrosion resistance of metallic copper. At the same time, the lysine-polyaspartic acid complex also has certain scale inhibition performance.

[0024] In summary, the present application has the following beneficial effects:

[0025] 1. Since the present application adopts the synergistic cooperation of benzotriazole, zinc gluconate, adipic dihydrazide and polyaspartic acid to form a protective film on the surface of metallic copper, slow down the corrosion efficiency of metallic copper, and thus improve the corrosion resistance of metallic copper.

[0026] 2. In this application, it is preferred to graft lysine with polyaspartic acid, which can form more coordination with metallic copper, form a protective film on the surface of metallic copper, and promote the more efficient anti-corrosion protection of metallic copper by the corrosion inhibitor. Detailed implementation manners

[0027] The following further elaborates on this application with reference to the examples.

[0028] In this specific implementation manner, under normal circumstances without other special conditions, the components used are as follows:

[0029] The molecular weight of polyaspartic acid is 4000.

[0030] Examples

[0031] Example 1

[0032] A highly corrosion-resistant BTA composite special copper corrosion inhibitor comprises the following raw materials in parts by weight: 17.5 kg of benzotriazole, 21 kg of sodium hydroxide, 4 kg of an auxiliary agent, 3.5 kg of polyaspartic acid, 5.5 kg of sodium tungstate, 6 kg of zinc gluconate, 2 kg of adipic dihydrazide, 65 kg of water, wherein the auxiliary agent is isopropanol.

[0033] A preparation method of a highly corrosion-resistant BTA composite special copper corrosion inhibitor comprises the following specific steps: First, mix polyaspartic acid, sodium tungstate, adipic dihydrazide, water and the auxiliary agent, heat to 80 °C, and stir at a speed of 800 r / min for 20 min to form a mixed solution A. Then, dropwise add zinc gluconate to the mixed solution A within 1 h, and mix and stir at a speed of 1500 r / min for 15 min to form a mixed solution B. Add sodium hydroxide to the mixed solution B, stir at a speed of 800 r / min for 5 min, and finally add benzotriazole, raise the temperature to 105 °C, reflux and react for 30 min, cool to 75 °C and then filter, and take the filtrate to cool down to obtain the highly corrosion-resistant BTA composite special copper corrosion inhibitor.

[0034] Examples 2 - 3

[0035] The differences between Examples 2 - 3 and Example 1 lie in that the contents of each component in the corrosion inhibitor raw materials are different, as shown in Table 1 specifically.

[0036] Table 1: Content table of each component in Examples 1 - 3

[0037]

[0038] Example 4

[0039] The difference between Example 4 and Example 1 lies in that the corrosion inhibitor raw materials further include 4 kg of sodium lignosulfonate.

[0040] A preparation method of a highly corrosion-resistant BTA composite special copper corrosion inhibitor includes the following specific steps: First, mix polyaspartic acid, sodium lignosulfonate, sodium tungstate, adipic dihydrazide, water and an auxiliary agent, heat to 80 °C, and stir at a speed of 800 r / min for 20 min to form a mixed solution A. Then, dropwise add zinc gluconate to the mixed solution A within 1 h, and mix and stir at a speed of 1500 r / min for 15 min to form a mixed solution B. Add sodium hydroxide to the mixed solution B, stir at a speed of 800 r / min for 5 min, and finally add benzotriazole, heat up to 105 °C, carry out a reflux reaction for 30 min, cool down to 75 °C and then filter, take the filtrate and cool it down to obtain the highly corrosion-resistant BTA composite special copper corrosion inhibitor.

[0041] Example 5

[0042] The difference between Example 5 and Example 4 is that the usage amount of sodium lignosulfonate in the corrosion inhibitor raw material is 3 kg.

[0043] Example 6

[0044] The difference between Example 6 and Example 4 is that the usage amount of sodium lignosulfonate in the corrosion inhibitor raw material is 5 kg.

[0045] Example 7

[0046] The difference between Example 7 and Example 4 is that the corrosion inhibitor raw material further includes 1.2 kg of lysine.

[0047] A preparation method of a highly corrosion-resistant BTA composite special copper corrosion inhibitor includes the following specific steps:

[0048] S1: Divide polyaspartic acid into two equal parts on average. Dissolve one part of polyaspartic acid in deionized water, and the mass ratio of deionized water to polyaspartic acid is 1:1 to form a polyaspartic acid solution. Then add lysine to the polyaspartic acid solution, heat it in an oil bath to 115 °C, react for 1.5 h, and then dry it at 60 °C to obtain a lysine-polyaspartic acid complex.

[0049] S2: Mix the remaining part of polyaspartic acid, lysine-polyaspartic acid complex, sodium lignosulfonate, sodium tungstate, adipic dihydrazide, water and an auxiliary agent, heat to 80 °C, and stir at a speed of 800 r / min for 20 min to form a mixed solution A. Then, dropwise add zinc gluconate to the mixed solution A within 1 h, and mix and stir at a speed of 1500 r / min for 15 min to form a mixed solution B. Add sodium hydroxide to the mixed solution B, stir at a speed of 800 r / min for 5 min, and finally add benzotriazole, heat up to 105 °C, carry out a reflux reaction for 30 min, cool down to 75 °C and then filter, take the filtrate and cool it down to obtain the highly corrosion-resistant BTA composite special copper corrosion inhibitor.

[0050] Example 8

[0051] The difference between Example 8 and Example 7 is that the usage amount of lysine in the corrosion inhibitor raw material is 0.5 kg.

[0052] Example 9

[0053] The difference between Example 9 and Example 7 is that the usage amount of lysine in the corrosion inhibitor raw material is 2 kg.

[0054] Example 10

[0055] The difference between Example 10 and Example 7 is that the corrosion inhibitor raw material further includes 2 kg of chitosan.

[0056] A preparation method of a highly corrosion-resistant BTA composite special copper corrosion inhibitor includes the following specific steps:

[0057] S1: Divide polyaspartic acid into two equal parts on average. Dissolve one part of polyaspartic acid in deionized water, and the mass ratio of deionized water to polyaspartic acid is 1:1 to form a polyaspartic acid solution. Then add lysine to the polyaspartic acid solution, heat it in an oil bath to 115 °C, react for 1.5 h, and then dry it at 60 °C to obtain a lysine-polyaspartic acid complex.

[0058] S2: Use hydrochloric acid and sodium hydroxide respectively to adjust the pH values of sodium lignosulfonate and chitosan to 5. Then put sodium lignosulfonate and chitosan into two centrifuge tubes respectively. After centrifuging for 15 min, take the supernatant of sodium lignosulfonate and slowly drip it into the supernatant of chitosan, react at room temperature for 30 min to form a composite liquid. Filter the composite liquid, wash it with deionized water, and finally dry it at 45 °C to obtain a sodium lignosulfonate-chitosan complex.

[0059] S3: Mix the remaining one part of polyaspartic acid, lysine-polyaspartic acid complex, sodium lignosulfonate-chitosan complex, sodium tungstate, adipic dihydrazide, water and additives, heat it to 80 °C, and stir it at a speed of 800 r / min for 20 min to form a mixed liquid A. Then drip zinc gluconate into the mixed liquid A within 1 h and mix and stir it at a speed of 1500 r / min for 15 min to form a mixed liquid B. Add sodium hydroxide to the mixed liquid B, stir it at a speed of 800 r / min for 5 min, and finally add benzotriazole, raise the temperature to 105 °C, reflux and react for 30 min, cool it to 75 °C and then filter, take the filtrate and cool it down to obtain a highly corrosion-resistant BTA composite special copper corrosion inhibitor.

[0060] Example 11

[0061] The difference between Example 11 and Example 10 is that the usage amount of chitosan in the corrosion inhibitor raw material is 1 kg.

[0062] Example 12

[0063] The difference between Example 12 and Example 10 is that the usage amount of chitosan in the corrosion inhibitor raw material is 3 kg.

[0064] Comparative Example

[0065] Comparative Example 1

[0066] The difference between Comparative Example 1 and Example 1 is that zinc gluconate in the corrosion inhibitor raw material is replaced with an equal amount of zinc sulfate.

[0067] Comparative Example 2

[0068] The difference between Comparative Example 2 and Example 1 is that polyaspartic acid is not used in the corrosion inhibitor raw material.

[0069] Comparative Example 3

[0070] The difference between Comparative Example 3 and Example 1 is that polyaspartic acid and sodium tungstate are not used in the corrosion inhibitor raw material.

[0071] Performance Detection Test

[0072] The following performance detections were carried out on the highly corrosion-resistant BTA composite special copper corrosion inhibitor provided by Examples 1-12 and Comparative Examples 1-3 of the present application, and the detection results are shown in Table 2.

[0073] Detection Method

[0074] I. Corrosion Inhibition Performance

[0075] Metal brass samples with dimensions of 10 mm×10 mm×10 mm were used, and the corrosion medium was 1 mol / L HCl solution. The brass samples were cleaned with ethanol, dried, weighed, and then all the samples were immersed in the corrosion medium and the corrosion medium containing the corrosion inhibitor prepared in the present application for 10 h. The mass fraction of the corrosion inhibitor in the corrosion medium was 3%, and the test temperature was 60°C. After the samples were corroded, they were cleaned with clean water, dried, weighed, the weight loss of the metal brass samples before and after corrosion was calculated, and the corrosion inhibition efficiency of the corrosion inhibitor of the present application was determined.

[0076] Table 2: Performance Detection Data Table

[0077]

[0078]

[0079] As can be seen from the performance test data sheet, the copper corrosion inhibitor prepared in this application has excellent and efficient corrosion inhibition performance, significantly reducing the corrosion rate of metallic copper. Each component in the corrosion inhibitor of this application cooperates synergistically with each other, can firmly adsorb on the surface of metallic copper, and can form a stable protective film on the metal surface, thereby playing a role in anti-corrosion protection for metallic copper and improving the corrosion resistance of metallic copper. In Examples 1-3 of this application, the contents of each component in the corrosion inhibitor are different. From the performance test results, it can be seen that each component in Example 1 can combine better.

[0080] In Examples 4-6, different amounts of sodium lignosulfonate are added to the corrosion inhibitor. From the performance test results, it can be seen that the corrosion inhibition performance of the corrosion inhibitor has been significantly improved. The multiple active groups on sodium lignosulfonate can form a stable complex with metal copper ions to form an insoluble protective film, thereby being able to protect metallic copper more stably and effectively. At the same time, sodium lignosulfonate and polyaspartic acid can also cooperate synergistically through the anode and cathode to form a dense surface film on the metal surface, inhibiting the corrosion of the corrosive medium to the metal matrix and further improving the corrosion inhibition effect of the corrosion inhibitor on metallic copper.

[0081] In Examples 7-9, different amounts of lysine are added to the corrosion inhibitor. From the performance test results, it can be seen that the corrosion inhibition efficiency of the corrosion inhibitor has been significantly improved. Lysine itself can have a certain adsorption with metallic copper, thereby forming a self-assembled film on the surface of metallic copper to further provide anti-corrosion protection for metallic copper. On the other hand, lysine can also react with the amide group of polyaspartic acid to modify polyaspartic acid, improving the corrosion inhibition efficiency of the corrosion inhibitor. At the same time, it is also found in actual use that the combination of lysine and polyaspartic acid has certain scale inhibition performance, enabling the corrosion inhibitor prepared in this application to have both corrosion inhibition performance and scale inhibition performance.

[0082] As can be seen from Examples 10-12, different amounts of chitosan are added to the corrosion inhibitor. From the performance test results, it can be seen that the corrosion inhibition efficiency of the corrosion inhibitor reaches 98%. Chitosan and sodium lignosulfonate form a polyelectrolyte complex through electrostatic interaction, improving the disordered structure of sodium lignosulfonate, and promoting sodium lignosulfonate and chitosan to form a uniform and stable protective film on the metal surface. Sodium lignosulfonate can also improve the crystallinity of chitosan. Therefore, sodium lignosulfonate and chitosan cooperate synergistically to further improve the corrosion inhibition efficiency of the corrosion inhibitor on metallic copper.

[0083] By comparing the performance test results of Comparative Example 1 and Example 1, it can be seen that in Comparative Example 1, zinc sulfate is used instead of zinc gluconate, and the corrosion inhibition efficiency of the corrosion inhibitor decreases significantly. This may be because the addition of zinc sulfate to the corrosion inhibitor is likely to cause a decrease in pH value, thereby promoting the anodic polarization of the metal and accelerating the dissolution of the metal.

[0084] From the performance test results of Comparative Examples 2 and 3 and Example 1, it can be seen that in Comparative Example 2, polyaspartic acid is not used, and in Comparative Example 3, neither polyaspartic acid nor sodium tungstate is used, and the corrosion inhibition efficiency of the corrosion inhibitor will decrease, and the corrosion inhibition efficiency of the corrosion inhibitor prepared in Comparative Example 3 is even lower. This may be because both sodium tungstate and polyaspartic acid have a certain corrosion inhibition effect on metallic copper, and the compounding of polyaspartic acid and sodium tungstate has a synergistic effect, which can form a passivation film on the surface of metallic copper and enhance the stability of the protective film, further improving the corrosion inhibition effect of the corrosion inhibitor on metallic copper.

[0085] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A highly corrosion-resistant BTA composite special copper corrosion inhibitor, characterized in that, It comprises the following raw materials in parts by weight: 10 - 25 parts of benzotriazole, 15 - 28 parts of sodium hydroxide, 3 - 5 parts of auxiliary agent, 2 - 5 parts of polyaspartic acid, 3 - 8 parts of sodium tungstate, 5 - 8 parts of zinc gluconate, 1 - 3 parts of adipic dihydrazide, 60 - 70 parts of water, 3 - 5 parts of sodium lignosulfonate, 0.5 - 2 parts of lysine, 1 - 3 parts of chitosan; the auxiliary agent is isopropanol.

2. A preparation method of the highly corrosion-resistant BTA composite special-effect copper corrosion inhibitor as described in claim 1, characterized in that: It comprises the following specific steps: S1: Divide polyaspartic acid into two equal parts on average. Dissolve one part of polyaspartic acid in deionized water, and the mass ratio of deionized water to polyaspartic acid is 1:1 to form a polyaspartic acid solution. Then add lysine to the polyaspartic acid solution, heat it in an oil bath to 115 °C, react for 1.5 h, and then dry it at 60 °C to obtain a lysine - polyaspartic acid complex. S2: Adjust the pH values of sodium lignosulfonate and chitosan to 5 respectively using hydrochloric acid and sodium hydroxide. Then put sodium lignosulfonate and chitosan into two centrifuge tubes respectively. After centrifuging for 15 min, take the supernatant of sodium lignosulfonate and slowly drip it into the supernatant of chitosan, react at room temperature for 30 min to form a composite solution, filter the composite solution, wash it with deionized water, and finally dry it at 45 °C to obtain a sodium lignosulfonate - chitosan complex. S3: Mix the remaining one part of polyaspartic acid, lysine - polyaspartic acid complex, sodium lignosulfonate - chitosan complex, sodium tungstate, adipic dihydrazide, water and auxiliary agent, heat it to 80 °C, stir at a speed of 800 r / min for 20 min to form a mixed solution A. Then add zinc gluconate dropwise to the mixed solution A within 1 h, mix and stir at a speed of 1500 r / min for 15 min to form a mixed solution B. Add sodium hydroxide to the mixed solution B, stir at a speed of 800 r / min for 5 min, and finally add benzotriazole, raise the temperature to 105 °C, reflux and react for 30 min, cool down to 75 °C and then filter. Take the filtrate, cool it down, and obtain a highly corrosion - resistant BTA composite special copper corrosion inhibitor.

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