Metal corrosion inhibitor component, method for preparing same, and use thereof

Abstract

The application discloses a metal corrosion inhibitor component, a preparation method and application thereof. The metal corrosion inhibitor component is a primary amine containing a tetraphenyl ethenyl sulfocyanate, which has excellent metal corrosion inhibition performance and is easy to detect the concentration in a corrosion medium. In addition, the compound can emit strong fluorescence after being adsorbed on a metal surface, which is beneficial to visual detection.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of metal corrosion inhibitor component and its preparation method and application, specifically to a kind of metal corrosion inhibitor component with fluorescence effect and its preparation method and application. BACKGROUND

[0002] Metal corrosion is a common problem in industrial production, and the safety accidents and unplanned shutdown accidents caused by metal corrosion have caused huge losses to enterprises. Metal corrosion prevention measures include material upgrading, process corrosion prevention and corrosion monitoring. Corrosion monitoring is the basis for realizing predictive maintenance and good process corrosion prevention.

[0003] Upgrading metal materials, selecting more corrosion-resistant metal materials is a method to slow down corrosion, but it is more economical to add metal corrosion inhibitor. Common metal corrosion inhibitors include organic amines, thiourea derivatives, imidazoline derivatives, acetylenic alcohols, benzotriazoles, etc. However, these metal corrosion inhibitors have their own shortcomings, such as poor corrosion inhibition performance and poor water solubility. Therefore, it is necessary to provide a corrosion inhibitor with better performance. The existing metal corrosion inhibitor is difficult to detect the effective concentration, and it is difficult to implement more targeted supplement measures. The current method is to periodically supplement the corrosion inhibitor, which is difficult to ensure the appropriate dosage of the agent. When the concentration of the agent is too high, it will be wasted, and when it is too low, it will not achieve the desired corrosion inhibition effect. In particular, it is more difficult to detect the adsorption degree of the existing metal corrosion inhibitor on the metal surface, and it is difficult to achieve predictive positioning maintenance and repair.

[0004] CN107973732A discloses a preparation method of an inhibitor component, its product and application. In the organic ammonium salt disclosed in this document, the maximum carbon number of the hydrocarbon group is 18. Generally speaking, a larger hydrocarbon group will result in a decrease in solubility and dispersibility in water, affecting the corrosion inhibition performance. In addition, this document does not disclose a hydrocarbon group containing multiple benzene rings, and the corrosion inhibitor component does not have a fluorescence effect.

[0005] The information disclosed in the foregoing background section is only used to strengthen the understanding of the background of the present application, and it can include information that is not known to those skilled in the art. SUMMARY

[0006] The present application provides a metal corrosion inhibitor component and its preparation method and application. The metal corrosion inhibitor component not only has good metal corrosion inhibition performance, but also is easy to detect the concentration in the corrosion medium, so corrosion protection can be more conveniently carried out. In addition, the metal corrosion inhibitor component also has a fluorescence effect when adsorbed on the metal surface, which can timely discover corrosion hazards and more efficiently prevent and reduce metal corrosion.

[0007] The main content of the present application is as follows:

[0008] 1. A metal corrosion inhibitor component, characterized in that it has the structure shown in formula I:

[0009]

[0010] wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; R1, R2 and R3 are each independently a hydrogen atom or an arbitrary substituent; m is 0 or 1, and n is 0 or 2.

[0011] 2. The metal corrosion inhibitor component according to any one of the preceding claims, wherein R1, R2 and R3 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that attached to the benzene ring ④.

[0012] 3. The metal corrosion inhibitor component according to any one of the preceding claims, wherein the substituents on the benzene rings (marked ①, ②, ③, ④) are all located at the para position of the vinyl group.

[0013] 4. The metal corrosion inhibitor component according to any one of the preceding claims, wherein m and n are both 0, one, two or all of R1, R2 and R3 are the same substituent as that attached to the benzene ring ④, and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group.

[0014] 5. A method for preparing a metal corrosion inhibitor component, comprising:

[0015] (1) reacting a compound represented by Formula II with an acid in a polar solvent;

[0016] (2) then adding a thiocyanate salt to react, forming a precipitate, and after removing the insoluble substances and the polar solvent produced in the reaction system, the metal corrosion inhibitor component is obtained.

[0017]

[0018] wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; R1', R2' and R3' are each independently a hydrogen atom or an arbitrary substituent; m is 0 or 1, and n is 0 or 2.

[0019] 8. The method for preparing according to any one of the preceding claims, wherein in the compound represented by Formula II, R1', R2' and R3' are each independently a hydrogen atom, a halogen atom, a hydroxy group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that attached to the benzene ring ④.

[0020] 9. The method for preparing according to any one of the preceding claims, wherein in the compound represented by Formula II, the substituents on the benzene rings (marked ①, ②, ③, ④) are all located at the para position of the vinyl group.

[0021] 10. The method for preparing according to any one of the preceding claims, wherein in the compound represented by Formula II, m and n are both 0, one, two or all of R1', R2' and R3' are the same substituent as that attached to the benzene ring ④, and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group.

[0022] 11. The method according to any one of the preceding claims, wherein the polar solvent is composed of 35% to 0% water and 65% to 100% water-miscible organic solvent.

[0023] 12. The method according to any one of the preceding claims, wherein the water-miscible organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane and ethylene glycol.

[0024] 13. The method according to any one of the preceding claims, wherein the amounts of the compound of formula II, the acid and the thiocyanate are in a ratio of 1:1:1, respectively, based on the total moles of the amino group, the acid dissociable hydrogen ion and the thiocyanate ion in the compound of formula II.

[0025] 14. The method according to any one of the preceding claims, wherein the thiocyanate is ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate.

[0026] 15. The method according to any one of the preceding claims, wherein the acid is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, phosphorous acid or hypophosphorous acid.

[0027] 16. The method according to any one of the preceding claims, wherein in step (1), the reaction temperature is from 20°C to 50°C and the reaction time is from 10 minutes to 2 hours.

[0028] 17. The method according to any one of the preceding claims, wherein in step (2), the reaction temperature is from 30°C to 100°C and the reaction time is from 20 minutes to 4 hours.

[0029] 18. A metal corrosion inhibitor component, wherein after the reaction in any one of the preceding methods, the insoluble matter is first removed by filtration, and then the solvent is removed or not removed, to obtain the metal corrosion inhibitor component.

[0030] 19. Use of the metal corrosion inhibitor component according to any one of the preceding claims in the field of protection against hydrogen evolution corrosion of metals.

[0031] 20. A metal corrosion inhibitor, comprising the metal corrosion inhibitor component according to any one of the preceding claims.

[0032] 21. A method for inhibiting corrosion of metals, wherein the corrosion medium contains the metal corrosion inhibitor component according to any one of the preceding claims.

[0033] 22. A method for protecting metal from corrosion, characterized in that the corrosion medium contains the metal corrosion inhibitor component of any one of the preceding claims, and the concentration of the metal corrosion inhibitor component in the corrosion medium is detected and controlled by UV-Vis absorption spectroscopy; preferably the concentration of the metal corrosion inhibitor component in the corrosion medium is controlled to be 40 mg / L to 160 mg / L.

[0034] 23. A method for protecting copper from corrosion, characterized in that the copper surface is adsorbed with the metal corrosion inhibitor component of any one of the preceding claims, and the copper surface is subjected to corrosion inhibition treatment in the area where there is no fluorescence or the fluorescence is weaker than in other areas under UV light irradiation.

[0035] The present application has the following beneficial technical effects:

[0036] I. Although the metal corrosion inhibitor component of the present application has a large tetraphenyl ethene group, it is easy to adsorb on the metal surface, and further has good performance in protecting the metal from corrosion.

[0037] II. Even if the metal corrosion inhibitor component of the present application is adsorbed and gathered on the metal surface, it can still emit strong visible fluorescence, so that when it is used as a metal corrosion inhibitor component, visual detection can be realized, and targeted metal corrosion protection can be realized.

[0038] III. The metal corrosion inhibitor component of the present application can detect the concentration in the corrosion medium, and can take more targeted supplement measures by detecting the concentration.

[0039] Other features and advantages of the present application will be described in detail in the specific embodiment part. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 NMR hydrogen spectrum of the product of Example 1.

[0041] Figure 2 Mass spectrum of the product of Example 1.

[0042] Figure 3 NMR hydrogen spectrum of the product of Example 2.

[0043] Figure 4 Mass spectrum of the product of Example 2.

[0044] Figure 5 UV-Vis absorption spectrum of the product of Example 2.

[0045] Figure 6 Photo of the test piece under UV light irradiation after the brass test piece corrosion test. DETAILED DESCRIPTION

[0046] The present application is described in detail below in conjunction with specific embodiments, but it should be noted that the scope of protection of the present application is not limited by these specific embodiments and the principle explanation, but is determined by the claims.

[0047] In the present application, any matter or item not mentioned explicitly, except for the content mentioned explicitly, directly applies to those known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solution or technical idea formed thereby is considered as part of the original disclosure or description of the present application, and should not be considered as new content not disclosed or anticipated herein, unless the combination is considered as obviously unreasonable by the person skilled in the art.

[0048] All the features disclosed in the present application can be combined arbitrarily, and these combinations should be understood as disclosed or described in the present application, and should be considered as specifically disclosed and described in the present application, unless the combination is considered as obviously unreasonable by the person skilled in the art. The numerical points disclosed in the specification include not only the numerical points specifically disclosed in the examples, but also the endpoints of the numerical ranges in the specification, and the ranges formed by the arbitrary combination of these numerical points should be considered as the ranges disclosed or described in the present application.

[0049] The technical and scientific terms in the present application are defined according to their definitions, and those not given definition are understood according to the usual meaning in the art.

[0050] The following are the definitions of some terms:

[0051] Hydrocarbon group, a group formed by removing one hydrogen atom from a hydrocarbon.

[0052] Alkyl group, a hydrocarbon group formed by removing one hydrogen atom from a saturated alkane molecule.

[0053] Aryl group, a hydrocarbon group formed by removing one hydrogen atom from an aromatic ring carbon.

[0054] Primary amine, a compound in which one hydrogen atom in an ammonia molecule is replaced by a hydrocarbon group or a substituted hydrocarbon group.

[0055] Precipitate, a substance generated by reaction and insoluble in the reaction solution.

[0056] In the present application, the corrosion medium refers to an acidic medium containing water or substantially water.

[0057] In the present application, when referring to the substituents on the benzene rings in the tetraphenyl ethylene derivative, it refers to the substituents on the four benzene rings of tetraphenyl ethylene except the vinyl group.

[0058] I. Metal corrosion inhibition component of the present application

[0059] The present application provides a metal corrosion inhibition component, which has the structure shown in formula I:

[0060]

[0061]

[0062] wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; R1, R2 and R3 are each independently a hydrogen atom or an arbitrary substituent; m is 0 or 1, and n is 0 or 2.

[0063] The metal corrosion inhibitor component according to the present application is easy to be adsorbed on the surface of metal and has metal corrosion inhibition performance, and the concentration thereof in a corrosion medium can be easily detected.

[0064] The metal corrosion inhibitor component according to the present application can emit strong fluorescence under excitation of ultraviolet light after being adsorbed on the surface of some metals, such as copper. Generally, fluorescence quenching occurs when a fluorescent substance is adsorbed on the surface of a metal. Some fluorescent substances have strong fluorescence in a dilute solution, but the fluorescence is weakened or disappears in a high concentration or aggregated state. However, the compound according to the present application can still emit strong visible fluorescence even if it is adsorbed and aggregated on the surface of a metal, so that visual detection can be achieved when the compound is used as a metal corrosion inhibitor. When used as a metal corrosion inhibitor, if uniform fluorescence is emitted from the surface of the metal, it indicates that a uniform and complete protective film is formed by the metal corrosion inhibitor, so that the metal corrosion inhibitor does not need to be supplemented. If no fluorescence or weak fluorescence is emitted from a certain area of the surface of the metal, it indicates that the metal corrosion inhibitor is not adsorbed on the area, a protective film is not formed, or the metal corrosion inhibitor is desorbed, the protective film is damaged, or the metal corrosion inhibitor is adsorbed in a small amount, so that the metal corrosion inhibitor only needs to be supplemented and the protective film only needs to be repaired, thereby saving the metal corrosion inhibitor and achieving efficient protection, so that targeted corrosion protection can be achieved.

[0065] In the metal corrosion inhibitor component according to the present application, R1, R2 and R3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that connected to the benzene ring (④). The hydrocarbon group can be an alkyl group, such as a methyl group, an ethyl group or a propyl group, or a cycloalkyl group. The hydrocarbon group can also be an aryl group, such as a phenyl group.

[0066] In the metal corrosion inhibitor component according to the present application, the substituents on the benzene rings (①, ②, ③ and ④) can be located at any position on the benzene rings, i.e. at the ortho position, the meta position or the para position of the vinyl group. Preferably, the substituents on the benzene ring (④) are located at the para position of the vinyl group. More preferably, all the substituents on the benzene rings are located at the para position of the vinyl group.

[0067] In a preferred embodiment of the metal corrosion inhibitor component according to the present application, m and n are both 0, one, two or all of R1, R2 and R3 are the same as the substituents on the benzene ring ④, and the remaining substituents are each independently a hydrogen atom or a C1-C4 alkyl group.

[0068] II. A method for preparing the metal corrosion inhibitor component

[0069] The present application also provides a method for preparing the aforementioned metal corrosion inhibitor component, comprising:

[0070] (1) reacting a compound represented by Formula II with an acid in a polar solvent;

[0071] (2) then adding a thiocyanate salt to generate a precipitate, and removing the insoluble substances and the polar solvent generated in the reaction system to obtain the compound.

[0072]

[0073] wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; R1', R2' and R3' are each independently a hydrogen atom or any substituent; m is 0 or 1, and n is 0 or 2.

[0074] According to the preparation method of the present application, the reaction is as shown below:

[0075]

[0076] According to the preparation method of the present application, in the compound represented by Formula II, R1', R2' and R3' are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that connected to the benzene ring ④.

[0077] According to the preparation method of the present application, the compound represented by Formula II can be obtained by commercial purchase or manufactured by any known method.

[0078] According to the preparation method of the present application, in the compound represented by Formula II, the substituents on the benzene rings (labeled as ①, ②, ③, ④) can be located at any position on the benzene ring, i.e. at the ortho position, the meta position or the para position of the vinyl group; preferably, the substituents on the benzene ring ④ are located at the para position of the vinyl group; more preferably, all the substituents on the benzene ring are located at the para position of the vinyl group.

[0079] According to the preparation method of the present application, in the compound represented by Formula II, m and n are both 0, one of R1', R2' and R3' is the same as the substituents on the benzene ring ④, and the remaining substituents are each independently a hydrogen atom or a C1-C4 hydrocarbon group; or two of R1', R2' and R3' are the same as the substituents on the benzene ring ④, and the remaining substituent is a hydrogen atom or a C1-C4 hydrocarbon group; or all of R1', R2' and R3' are the same as the substituents on the benzene ring ④.

[0080] According to the preparation method of the present application, the polar solvent is composed of 35v% to 0v% water and 65v% to 100v% water-miscible organic solvent, preferably 25v% to 4v% water and 75v% to 96v% water-miscible organic solvent.

[0081] According to the preparation method of the present application, the water-miscible organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane and ethylene glycol.

[0082] According to the preparation method of the present application, the amount of acid and thiocyanate is determined relative to the amount of substance of the amino group in the compound of formula II. Those skilled in the art can determine the appropriate amount of substance ratio by simple tests according to the needs of the reaction. According to the preparation method of the present application, the amount ratio between the compound of formula II, the acid and the thiocyanate is about 1:1:1, respectively, based on the total moles of the amino group in the compound of formula II, the dissociable hydrogen ion of the acid and the thiocyanate ion.

[0083] According to the preparation method of the present application, the thiocyanate is ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate.

[0084] According to the preparation method of the present application, the acid is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, phosphorous acid or hypophosphorous acid.

[0085] According to the preparation method of the present application, in step (1), the reaction temperature is 20°C to 50°C and the reaction time is 10 minutes to 2 hours.

[0086] According to the preparation method of the present application, in step (2), the reaction temperature is 30°C to 100°C and the reaction time is 20 minutes to 4 hours.

[0087] In some embodiments, the compound of formula II is 4-amino-tetraphenyl ethene, di-(4-amino)-tetraphenyl ethene (cis or trans), tri-(4-amino)-tetraphenyl ethene, tetra-(4-amino)-tetraphenyl ethene or 4-(2-amino)ethoxy-tetraphenyl ethene.

[0088] According to the preparation method of the present application, any method for removing the insoluble matter and the solvent from the reaction system can be used, but a simple method is to first remove the insoluble matter by filtration, and then evaporate the polar solvent.

[0089] The present application also provides a metal corrosion inhibitor component: in the aforementioned method, after the reaction is completed, the insoluble matter is first removed by filtration, and the solvent can be removed, partially removed or not removed, thereby obtaining the metal corrosion inhibitor component.

[0090] Three, the application of the metal corrosion inhibitor component of the present application

[0091] The present application provides the application of any of the aforementioned metal corrosion inhibitor components in the field of metal hydrogen evolution corrosion protection.

[0092] According to the application of the present application, any of the aforementioned metal corrosion inhibitor components is suitable for environments where hydrogen evolution corrosion exists, and particularly suitable for environments where hydrogen evolution corrosion is the main or only corrosion.

[0093] According to the application of the present application, any of the aforementioned metal corrosion inhibitor components is used in a strongly acidic environment. The strongly acidic environment can be an aqueous phase containing strong acids of different concentrations, such as an aqueous phase containing one or more of sulfuric acid, hydrochloric acid, mud acid, and sulfamic acid. The strong acidity can be pH < 3.

[0094] According to the application of the present application, any of the aforementioned metal corrosion inhibitor components is used in a weakly acidic environment. The weakly acidic environment can be an aqueous phase containing weak acids of different concentrations, such as an aqueous phase containing one or more of formic acid, acetic acid, and citric acid, or an aqueous phase dissolved with one or more of CO2, H2S, SO2, etc. In the present application, the weak acidity can be pH 3-7.

[0095] The present application provides a metal corrosion inhibitor containing any of the aforementioned metal corrosion inhibitor components.

[0096] The present application also provides a metal corrosion method, wherein the corrosion medium contains any of the aforementioned metal corrosion inhibitor components. The concentration of any of the aforementioned metal corrosion inhibitor components in the corrosion medium can be controlled at 40-160 mg / L, preferably 60-140 mg / L, and more preferably 70-120 mg / L.

[0097] The present application also provides another metal corrosion method, wherein the corrosion medium contains any of the aforementioned metal corrosion inhibitor components, and the total concentration of any of the aforementioned metal corrosion inhibitor components in the corrosion medium is detected and controlled by ultraviolet-visible absorption spectroscopy. Preferably, the total concentration of any of the aforementioned metal corrosion inhibitor components in the corrosion medium is detected by ultraviolet-visible absorption spectroscopy and controlled at 40-160 mg / L.

[0098] The present application also provides a copper corrosion protection method, wherein the copper surface is adsorbed with any of the aforementioned metal corrosion inhibitor components, and the copper surface is subjected to corrosion treatment by fluorescence of the copper surface under ultraviolet light irradiation, and the area without fluorescence or with weaker fluorescence than other areas is subjected to corrosion treatment.

[0099] According to the copper corrosion protection method of the present application, the corrosion treatment is to supplement the adsorption of any of the aforementioned metal corrosion inhibitor components.

[0100] The copper corrosion protection method according to the present application can realize positioning corrosion protection by positioning and adding corrosion inhibitor and repairing the protective film in the area where the corrosion inhibitor is not adsorbed, the protective film is not formed or the corrosion inhibitor desorption occurs and the protective film is incomplete. This can be easily realized on the metal surface plane, and even in the inner wall of the metal pipeline, with the aid of an endoscopic ultraviolet light source and a dosing facility, the purpose of detection and directional dosing can be achieved.

[0101] The present application will be described in detail below with reference to specific examples. The following examples will help those skilled in the art to further understand the present application, but do not limit the present application in any form.

[0102] Instruments and tests

[0103] In the examples, nuclear magnetic analysis (1H NMR) was performed using a Bruker Avance 400MHz nuclear magnetic resonance spectrometer; mass spectrometry (ESI-MS) was performed using a Bruker Solarix FT-ICR MS Fourier transform ion cyclotron resonance mass spectrometer; and ultraviolet-visible absorption spectrum analysis was performed using a Perkin Elmer Lambda 750 ultraviolet spectrophotometer.

[0104] Example 1

[0105] The preparation method is as follows.

[0106]

[0107] The specific steps are as follows: 10 mL of methanol / acetone / water (v / v / v = 45 / 45 / 10), 0.695 g of 4-aminotetraphenyl ethylene (0.002 mol) were added to a 50 mL flask, 0.2 g of concentrated HCl (0.002 mol) was slowly dropped into the flask under stirring at 20°C, and the reaction was stirred for 20 min. 0.152 g of ammonium thiocyanate (0.002 mol) was dissolved in 5 mL of methanol / acetone / water (v / v / v = 45 / 45 / 10) and added to the flask, which produced a white precipitate, and the temperature was raised to 40°C, and the reaction was carried out for 2 h. After the reaction was completed, the temperature was cooled to room temperature, and the layers were separated after standing, the upper layer was a yellow clear solution, and the lower layer was a white precipitate. The collected yellow clear solution was spin-dried to obtain 0.795 g of yellow solid, which was the target product.

[0108] 1H NMR (400 MHz, DMSO): δ 7.30-6.85 (19H, m).

[0109] MS (ESI-MS): [M-H + ] 347.1684.

[0110] Example 2

[0111] Preparation method is as follows.

[0112]

[0113] Specific steps are: 10 mL of ethanol / tetrahydrofuran / water (v / v / v = 70 / 26 / 4), 0.725 g of bis-(4-amino)-tetraphenyl ethylene (0.002 mol) is added to a 50 mL flask, 0.2 g of concentrated H2SO4 (0.002 mol) is slowly dropped into 50 ℃ stirring, and stirring is reacted for 2 h. 0.325 g of sodium thiocyanate (0.004 mol) is dissolved in 5 mL of ethanol / tetrahydrofuran / water (v / v / v = 70 / 26 / 4), and is added to the flask, a white precipitate is generated, the temperature is raised to 80 ℃, and reaction is carried out for 20 min. After the reaction is completed, it is cooled to room temperature, and is left to separate into layers, the upper layer is a yellow clear solution, and the lower layer is a white precipitate. Filtration is carried out, and the collected yellow clear solution is spin-dried to obtain 0.945 g of a yellow solid, which is the target product.

[0114] 1H NMR (400 MHz, DMSO): δ 7.20-7.11 (6H, m), 7.10-7.03 (8H, m), 7.01-6.95 (4H, d).

[0115] MS (ESI-MS): [M-H + ] 363.18574, [M-2H + + Na + ] 385.16772.

[0116] Example 3

[0117] Preparation method is as follows.

[0118]

[0119] Specific steps are: 10 mL of ethanol / tetrahydrofuran / water (v / v / v = 70 / 26 / 4), 0.725 g of bis-(4-amino)-tetraphenyl ethylene (0.002 mol) is added to a 50 mL flask, 0.2 g of concentrated H2SO4 (0.002 mol) is slowly dropped into 50 ℃ stirring, and stirring is reacted for 2 h. 0.325 g of sodium thiocyanate (0.004 mol) is dissolved in 5 mL of ethanol / tetrahydrofuran / water (v / v / v = 70 / 26 / 4), and is added to the flask, a white precipitate is generated, the temperature is raised to 80 ℃, and reaction is carried out for 20 min. After the reaction is completed, it is cooled to room temperature, and is left to separate into layers, the upper layer is a yellow clear solution, and the lower layer is a white precipitate. Filtration is carried out, and the collected yellow clear solution is spin-dried to obtain 0.945 g of a yellow solid, which is the target product.

[0120] Example 4

[0121] The preparation method is shown in the following formula.

[0122]

[0123] The specific steps are as follows: 10 mL of N,N-dimethylformamide / water (v / v = 80 / 20) and 0.783 g of 4-(2-amino)ethoxytetraphenylene (0.002 mol) were added to a 50 mL three-necked flask. 0.2 g of concentrated HCl (0.002 mol) was slowly added dropwise under stirring at 20 °C, and the reaction was continued for 30 min. 0.162 g of sodium thiocyanate (0.002 mol) was dissolved in 5 mL of N,N-dimethylformamide / water (v / v = 80 / 20) and added to the three-necked flask, resulting in a white precipitate. The temperature was raised to 100 °C, and the reaction was continued for 2 h. After the reaction was complete, the mixture was cooled to room temperature and allowed to stand for phase separation. The upper layer was a clear brownish-yellow solution, and the lower layer was a white precipitate. The mixture was filtered, and the collected clear brownish-yellow solution was evaporated to dryness to obtain 0.857 g of a brownish-yellow solid, which is the target product.

[0124] Example 5

[0125] Rotary Coupling Corrosion Test

[0126] Preparation of the corrosion solution: Dissolve 208g of concentrated H2SO4 in 4L of deionized water to obtain a 0.5M H2SO4 solution. Then, take 250mL of the 0.5M H2SO4 solution into different glass bottles. Suspend metal test pieces, which have been treated with ethanol and weighed, in these glass bottles in sequence, with the test pieces immersed in the solution but not touching the bottom or wall of the bottle. One bottle is left untreated as a blank test (i.e., Comparative Example 0). Add a certain concentration of the corrosion inhibitor product prepared in the previous examples (i.e., Examples 1 to 4) to each bottle, and add a certain concentration of the aminotetraphenyl raw material from the previous examples (i.e., Comparative Examples 1 to 4) to each bottle. Place the glass bottles containing the corrosion solution and test pieces into a rotary sampler. Set the temperature of the rotary sampler to 60℃, the rotation speed to 28r / min, and the linear velocity to 1m / s. After a certain period of time, the test is completed. The test pieces are removed, treated with water, ethanol, etc., and then weighed. Calculate the mass loss of the test pieces before and after the test to obtain the corrosion inhibition performance of the agent.

[0127] The formula for calculating corrosion inhibition rate is as follows:

[0128] η=(Δm0-Δm1) / Δm0×100

[0129] In the formula: η—corrosion inhibition rate, %

[0130] Δm0—Mass loss of the specimen in the blank test, in g

[0131] Δm1—Mass loss of the test piece during the dosing test, in g

[0132] The rotating coupon corrosion test was carried out on two metal coupons of H62 brass and N80 carbon steel in the same way, except that the test time was different, 72 h for brass and 4 h for carbon steel. The results of brass coupons are shown in Table 1, and the results of carbon steel coupons are shown in Table 2.

[0133] The results of Table 1 show that for brass, the corrosion inhibition rate of the corrosion inhibition component of the present application gradually increases with the increase of the concentration of the agent. When the concentration of the agent is 100 mg / L, the corrosion inhibition rate of Examples 1 to 4 all exceeds 75%, among which the corrosion inhibition rate of Example 2 exceeds 99%, and the corrosion inhibition performance is good; while the aminotetraphenyl ethylene raw material used, i.e. Comparative Examples 1 to 4, has almost no corrosion inhibition performance, and may even slightly aggravate corrosion.

[0134] The results of Table 2 show that for carbon steel, the corrosion inhibition rate of the corrosion inhibition component of the present application gradually increases with the increase of the concentration of the agent. When the concentration of the agent is 100 mg / L, the corrosion inhibition rate of Examples 1 to 4 all exceeds 75%, among which the corrosion inhibition rate of Example 2 exceeds 97%, and the corrosion inhibition performance is good; while the aminotetraphenyl ethylene raw material used, i.e. Comparative Examples 1 to 4, has almost no corrosion inhibition performance, and may even slightly aggravate corrosion.

[0135] Table 1

[0136] Concentration of agent 40 mg / L 70 mg / L 100 mg / L Comparative Example 0 - - - Example 1 56.3％ 63.4％ 77.0％ Example 2 96.3％ 98.1％ 99.9％ Example 3 87.8％ 91.8％ 95.6％ Example 4 58.6％ 68.1％ 79.3％ Comparative Example 1 : 4-amino-tetraphenyl ethene 2.5％ 7.7％ 5.2％ Comparative Example 2: di-(4-amino)-tetraphenyl ethene 0.3％ 17.8％ 10.8％ Comparative Example 3: tetra-(4-amino)-tetraphenyl ethene 1.1％ -2.1％ 8.3％ Comparative Example 4: 4-(2-amino)ethoxy-tetraphenyl ethene -7.9％ 4.6％ 1.3％

[0137] Table 2

[0138] Concentration of agent 40 mg / L 70 mg / L 100 mg / L Comparative Example 0 - - - Example 1 32.2％ 53.5％ 76.3％ Example 2 95.2％ 96.8％ 97.3％ Example 3 95.6％ 97.5％ 97.8％ Example 4 34.6％ 56.8％ 78.2％ Comparative Example 1 : 4-amino-tetraphenyl ethene 3.3％ 6.8％ 6.1％ Comparative Example 2: di-(4-amino)-tetraphenyl ethene 1.7％ 11.2％ 8.3％ Comparative Example 3: tetra-(4-amino)-tetraphenyl ethene -2.5％ -0.9％ 5.2％ Comparative Example 4: 4-(2-amino)ethoxy-tetraphenyl ethene -2.9％ -8.3％ 3.7％

[0139] Example 6

[0140] This example is used to illustrate the determination of the concentration of the metal corrosion inhibition component of the present application in the corrosion medium. Taking the product of Example 2 as an example, it is prepared into solutions with different mass concentrations with 0.5 M H2SO4 as the solvent, and the ultraviolet-visible absorption spectrum is determined, as shown in Figure 5 It can be seen that the compound has obvious ultraviolet absorption peak, and the absorbance Abs at the wave peak of 300 nm is linearly fitted with the mass concentration c to obtain the relationship Abs = 0.03767c - 0.00825. When the corrosion medium contains the compound with unknown concentration, the ultraviolet-visible absorption spectrum of the solution is determined to obtain the absorbance at 300 nm, and the mass concentration of the compound in the corrosion medium can be determined by substituting the above relationship. If the concentration is too large and the absorbance exceeds the range, it can be diluted and then determined.

[0141] Example 7

[0142] This example is used to illustrate the fluorescence of the compound of the present application adsorbed on the surface of copper.

[0143] After the end of the corrosion test of Example 5 brass coupons, the surfaces of the coupons of Examples 1 to 4 adsorbed the corrosion inhibitor component product, and the coupons presented a certain intensity of fluorescence under 365 nm ultraviolet light irradiation; the coupon of Comparative Example 0 without adding any medicament presented no fluorescence under 365 nm ultraviolet light irradiation; the coupons of the amino tetraphenyl ethene raw material (Comparative Examples 1 to 4) with almost no corrosion inhibition performance presented no fluorescence under 365 nm ultraviolet light irradiation. Figure 6 From left to right, the photos are of Comparative Example 0, 100 mg / L Comparative Example 1, 100 mg / L Comparative Example 2, 100 mg / L Comparative Example 3, 100 mg / L Comparative Example 4, 100 mg / L Example 1, 100 mg / L Example 2, 100 mg / L Example 3, 100 mg / L Example 4 after the end of the corrosion test under 365 nm ultraviolet light irradiation. It can be seen that the corrosion inhibitor component of the present application has a visual detection effect.

Claims

1. A metal corrosion inhibiting composition characterized in that, having the structure shown in Formula I: wherein X is an oxygen atom; R1, R2 and R3 are each independently a hydrogen atom or the same as the substituent connected to the benzene ring ④; m is 0 and n is 0, or m is 1 and n is 2.

2. The metal corrosion inhibiting composition according to claim 1, characterized in that, The substituents on the benzene ring are all located at the para position of the vinyl group.

3. The metal corrosion inhibiting composition according to claim 1, wherein m and n are both 0, one, two or all of R1, R2 and R3 are the same as the substituent on the benzene ring ④, and the rest are hydrogen atoms.

4. A method for preparing a metal corrosion inhibitor component, comprising: (1) reacting a compound shown in Formula II with an acid in a polar solvent; (2) then adding a thiocyanate salt to react, forming a precipitate, and after removing the insoluble substances and the polar solvent produced in the reaction system, the metal corrosion inhibitor component is obtained; wherein X is an oxygen atom; R1, R2 and R3 are each independently a hydrogen atom or the same as the substituent connected to the benzene ring ④; m is 0 and n is 0, or m is 1 and n is 2.

5. The production method according to claim 4, characterized by, In the compound shown in Formula II, the substituents on the benzene ring are all located at the para position of the vinyl group.

6. The production method according to claim 4, characterized by, In the compound shown in Formula II, m and n are both 0, one, two or all of R1, R2 and R3 are the same as the substituent on the benzene ring ④, and the rest are hydrogen atoms.

7. The preparation method according to claim 4, characterized in that, The polar solvent is composed of 35v% to 0v% water and 65v% to 100v% water-miscible organic solvent.

8. The method of claim 7, wherein the step of forming the first and second layers is performed by a method comprising: The water-miscible organic solvent is one or several of methanol, ethanol, n-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane and ethylene glycol.

9. The production method according to claim 4, characterized by, The thiocyanate salt is ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate.

10. The preparation method according to claim 4, characterized in that, The acid is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, phosphorous acid or hypophosphorous acid.

11. A metal corrosion inhibiting composition characterized in that, In any of the methods of claims 4 to 10, after the reaction is completed, insoluble substances are first removed by filtration, and then the solvent is removed or not removed, and the metal corrosion inhibitor component is obtained.

12. Use of any of the metal corrosion inhibitor components of claims 1 to 3 and 11 in the field of protection against hydrogen evolution corrosion of metals.

13. A metal corrosion inhibitor characterized by, containing any of the metal corrosion inhibitor components of claims 1 to 3 and 11.

14. A method of metal corrosion inhibition, characterized by, containing any of the metal corrosion inhibitor components of claims 1 to 3 and 11.

15. A method of metal corrosion inhibition, characterized in that, containing any of the metal corrosion inhibitor components of claims 1 to 3 and 11 in the corrosion medium, and the concentration of the metal corrosion inhibitor component in the corrosion medium is detected and controlled by ultraviolet-visible absorption spectroscopy.

16. A method for the corrosion protection of copper, characterized in that The copper surface is adsorbed with any of the metal corrosion inhibitor components of claims 1 to 3 and 11, and the area without fluorescence or with weaker fluorescence than other areas on the copper surface is subjected to corrosion inhibition treatment by ultraviolet light irradiation.

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