A compound and its preparation method and application

Abstract

The present invention discloses a compound, its preparation method, and application. The compound has a structure in which a nitrogen atom links an ethylamine group or a polyethylene polyamine group with a tetraphenylethylene group. The compound readily adsorbs onto metal surfaces and exhibits excellent metal corrosion inhibition properties. Furthermore, the compound exhibits a fluorescence effect, making its concentration in corrosive media easily detectable.

Description

Technical Field

[0001] The present invention relates to a compound, a preparation method and application thereof, and in particular to a compound with a fluorescent effect, a preparation method thereof and application thereof in metal corrosion protection. Background Art

[0002] Metal corrosion is a common problem in industrial production, resulting in significant losses for businesses due to safety incidents and unplanned downtime. Metal corrosion prevention measures include material upgrades, process corrosion prevention, and corrosion monitoring. Corrosion monitoring is the foundation for predictive maintenance and effective process corrosion prevention.

[0003] Upgrading metal materials and choosing more corrosion-resistant metal materials is one way to slow down corrosion, but adding metal corrosion inhibitors is more economical. Common metal corrosion inhibitors include organic amines, thiourea derivatives, imidazoline derivatives, acetylenic alcohols, benzotriazole, etc., but these metal corrosion inhibitors each have shortcomings, such as unsatisfactory corrosion inhibition performance and poor water solubility. Therefore, it is necessary to provide corrosion inhibitors with more advantages in performance or new features. The effective concentration of existing metal corrosion inhibitors is not easy to detect, and it is difficult to implement more targeted replenishment measures. The current method is to periodically add corrosion inhibitors in a quantitative manner, which makes it 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, the required corrosion inhibition effect will not be achieved. In particular, it is even more difficult to detect the degree of adsorption of existing metal corrosion inhibitors on the metal surface, making it difficult to achieve predictive positioning maintenance and repairs.

[0004] The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not known to one of ordinary skill in the art. Summary of the Invention

[0005] One of the objects of the present invention is to provide a new compound with metal corrosion inhibition function and a preparation method thereof. The second object of the present invention is to provide a metal corrosion inhibition component and a metal corrosion inhibition method thereof, which is applicable to hydrogen evolution corrosion of metals. The third object of the present invention is to provide a method for corrosion monitoring and corrosion prevention, in which the concentration of the metal corrosion inhibition component in the corrosive medium is easily detected, so that corrosion protection can be carried out more conveniently. The fourth object of the present invention is to provide a method for corrosion protection, which utilizes the fluorescence effect of the metal corrosion inhibition component adsorbed on the metal surface to timely discover corrosion hazards, carry out fixed-point and positioned corrosion protection, and more efficiently prevent or reduce the occurrence of metal corrosion.

[0006] To achieve the above objectives, the present invention provides the following solutions:

[0007] 1. A compound characterized by having the structure shown in Formula I:

[0008]

[0009] wherein n is 0 to 50; and R1, R2 and R3 are each independently a hydrogen atom or an arbitrary substituent.

[0010] 2. The compound according to 1, wherein n is 0-30, preferably 0-16, and more preferably 0-12.

[0011] 3. A compound according to any of the preceding claims, wherein R1, R2 and R3 are each independently a hydrogen atom, a hydrocarbon group or the same as the substituent on the benzene ring ④.

[0012] 4. A compound according to any of the preceding claims, characterized in that the substituents on the benzene ring (marked as ①, ②, ③, ④) are all located in the para position relative to the vinyl group.

[0013] 5. A compound according to any of the preceding claims, wherein R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group; n is 4 to 12; or

[0014] One of R1, R2 and R3 is the same as the substituent on the benzene ring ④, and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group; n is 2 to 12; or

[0015] Two of R1, R2 and R3 are the same as the substituents on the benzene ring ④; the remaining substituents are hydrogen atoms or hydrocarbon groups; n is 0 to 12; or

[0016] R1, R2 and R3 are the same as the substituents on the benzene ring ④; n is 0 to 12.

[0017] 6. A method for preparing a compound, comprising: reacting a compound represented by Formula II with a compound represented by Formula III in the absence of a solvent or in an organic solvent in the presence of copper powder;

[0018]

[0019] Wherein, R1', R2' and R3' are each independently a hydrogen atom or an arbitrary substituent, X is -Cl, -Br or -I; and n is 0-50.

[0020] 8. A method according to any of the above, characterized in that n is 0-30, preferably 0-16, more preferably 0-12.

[0021] 9. A preparation method according to any of the above, characterized in that, in the compound represented by formula II, the substituents on the benzene ring (marked as ①, ②, ③, ④) are all located in the para position of the vinyl group.

[0022] 10. A preparation method according to any of the foregoing, characterized in that, in the compound of formula II, one of R1', R2' and R3' is the same as the substituent on the benzene ring ④, and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group; or two of R1', R2' and R3' are the same as the substituent on the benzene ring ④, and the remaining substituents are hydrogen atoms or hydrocarbon groups; or all of R1', R2' and R3' are the same as the substituents on the benzene ring ④.

[0023] 11. A method according to any of the above preparations, characterized in that the reaction temperature is 80°C to 200°C.

[0024] 12. A preparation method according to any of the above, characterized in that the reaction time is 2h to 168h.

[0025] 13. A preparation method according to any of the above, characterized in that the molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.01-1):(1-100), preferably 1:(0.03-0.5):(1.5-30).

[0026] 14. A preparation method according to any of the above, characterized in that the reaction solvent is 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

[0027] 15. A metal corrosion inhibition component, characterized in that it is prepared by any of the above methods.

[0028] 16. Use of any of the aforementioned compounds or the metal corrosion inhibition component of 15 in the field of metal hydrogen evolution corrosion protection.

[0029] 17. A metal corrosion inhibitor, characterized by containing any of the aforementioned compounds or the metal corrosion inhibition component of 15.

[0030] 18. A metal corrosion inhibition method, characterized in that the corrosive medium contains any of the aforementioned compounds or the metal corrosion inhibition component of 15.

[0031] 19. A metal corrosion inhibition method, characterized in that the corrosive medium contains any of the aforementioned compounds, and the concentration of the compound in the corrosive medium is detected and controlled by ultraviolet-visible absorption spectroscopy; preferably, the concentration of the compound in the corrosive medium is controlled at 40 mg / L to 160 mg / L.

[0032] 20. A method for protecting copper from corrosion, characterized in that any of the aforementioned compounds is adsorbed on the copper surface, and the fluorescence of the copper surface under ultraviolet light is used to perform corrosion inhibition treatment on areas of the copper surface that have no fluorescence or have weaker fluorescence than other areas.

[0033] The present invention has the following beneficial technical effects:

[0034] 1. The compound of the present invention has a relatively large tetraphenylethylene group, but is easily adsorbed on the metal surface, thereby having excellent performance in protecting metal corrosion, and is a highly effective metal corrosion inhibition component.

[0035] Second, the concentration of the compound of the present invention in the corrosive medium can be easily detected, and by detecting the concentration, more targeted supplementary measures can be taken.

[0036] 3. Even if the compound of the present invention is adsorbed and accumulated on the metal surface, it can still emit strong visible fluorescence, so that when it is used as a metal corrosion inhibition component, visual detection can be achieved, and targeted metal corrosion protection can be achieved.

[0037] Other features and advantages of the present invention will be described in detail in the detailed description section. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product in Example 1.

[0039] Figure 2 This is the mass spectrum of the product of Example 1.

[0040] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the product in Example 2.

[0041] Figure 4 This is the mass spectrum of the product of Example 2.

[0042] Figure 5 This is the UV-visible absorption spectrum of the product in Example 2.

[0043] Figure 6 This is a photo of the brass specimen under ultraviolet light after the corrosion test. DETAILED DESCRIPTION

[0044] The present invention is described in detail below in conjunction with specific embodiments. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments and principle explanations, but is determined by the claims.

[0045] In the present invention, except for the contents explicitly described, any matters or issues not mentioned are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical concepts formed thereby are considered part of the original disclosure or description of the present invention and should not be regarded as new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0046] All features disclosed in this invention may be combined in any combination, and such combinations should be understood as disclosed or described in this invention. Unless a person skilled in the art considers such combination to be obviously unreasonable, such combinations should be considered as specifically disclosed and described in this invention. The numerical values ​​disclosed in this specification include not only the numerical values ​​specifically disclosed in the examples, but also the endpoints of the numerical ranges in this specification. The ranges of any combination of these numerical values ​​should be considered as the ranges disclosed or described in this invention.

[0047] Technical and scientific terms in the present invention shall be understood according to their definitions if they are defined, and shall be understood according to their general meanings in the art if they are not defined.

[0048] In the present invention, ethylamino refers to -CH2CH2NH2.

[0049] In the present invention, polyethylene polyamine refers to -(CH2CH2NH) m H,m>1.

[0050] In the present invention, the corrosive medium refers to an acidic medium containing water or consisting essentially of water.

[0051] In the present invention, when referring to the substituents on the benzene rings of the tetraphenylethylene derivative, it refers to the substituents on the four benzene rings of the tetraphenylethylene except the vinyl group.

[0052] 1. Compounds of the Present Invention

[0053] The present invention provides a compound having the structure shown in Formula I:

[0054]

[0055] wherein n is 0 to 50; and R1, R2 and R3 are each independently a hydrogen atom or an arbitrary substituent.

[0056] According to the present invention, it has been discovered that the structure of "a nitrogen atom linking an ethylamine group or a polyethylene polyamine group to a tetraphenylethylene group" makes the compound easily adsorbed on metal surfaces, making it useful as a highly effective metal corrosion inhibitor. The compound of the present invention, based on the above basic structure, possesses excellent metal corrosion inhibition properties. Therefore, there are no particular limitations on the type and number of R1, R2, and R3. Based on the teachings of the present invention, those skilled in the art can select suitable raw materials to produce the compound of the present invention based on cost and practical considerations.

[0057] According to the compound of the present invention, after being adsorbed on certain metal surfaces, such as copper surfaces, it can emit strong fluorescence under ultraviolet light excitation. Fluorescence quenching may occur when general fluorescent substances are adsorbed on metal surfaces; some fluorescent substances have strong fluorescence in dilute solutions, but the fluorescence will weaken or disappear at high concentrations or in aggregated states. However, even if the compound of the present invention is adsorbed and aggregated on the metal surface, it can still emit strong visible fluorescence, so that visual detection can be achieved when it is used as a metal corrosion inhibition component. When used as a metal corrosion inhibitor, if uniform fluorescence is emitted everywhere on the metal surface, it indicates that the metal corrosion inhibitor has formed a uniform and complete protective film, and there is no need to add corrosion inhibitor at this time; if there is no fluorescence or weak fluorescence in a certain area of ​​the metal surface, it indicates that the corrosion inhibitor has not been adsorbed in this area, no protective film has been formed, or corrosion inhibitor desorption has occurred, the protective film is incomplete, or the corrosion inhibitor is less adsorbed, then it is only necessary to locate the corrosion inhibitor and repair the protective film, which saves reagents and can provide efficient protection, thereby achieving localized corrosion protection.

[0058] According to the compound of the present invention, n is preferably 0-30, more preferably 0-16, and even more preferably 0-12.

[0059] According to the compounds of the present invention, R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group; the hydrocarbon group may be an alkyl group, a chain alkyl group such as a methyl group, an ethyl group or a propyl group, or a cycloalkyl group; the hydrocarbon group may also be an aryl group such as a phenyl group.

[0060] According to the compounds of the present invention, the substituents on the benzene ring (marked as ①, ②, ③, ④) can be located at any position on the benzene ring, that is, at the ortho, meta or 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 substituents on the benzene ring are located at the para position of the vinyl group.

[0061] According to the compound of the present invention, in one embodiment, R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group, preferably R1, R2 and R3 are all hydrogen atoms; and n is preferably 4-12.

[0062] According to the compound of the present invention, another embodiment is: one of R1, R2 and R3 is the same as the substituent on the benzene ring ④ (preferably, the position on the benzene ring is also the same relative to the vinyl group), and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group; preferably, the remaining substituents are all hydrogen atoms; n is preferably 2 to 12.

[0063] According to the compound of the present invention, another embodiment is: two of R1, R2 and R3 are the same as the substituents on the benzene ring ④ (preferably, the positions on the benzene ring are also the same relative to the vinyl group); the remaining substituents are hydrogen atoms or hydrocarbon groups, more preferably hydrogen atoms; n is preferably 0 to 12.

[0064] According to another embodiment of the compound of the present invention, R1, R2 and R3 are the same as the substituents on the benzene ring ④ (preferably, the positions on the benzene ring are also the same relative to the vinyl group); and n is preferably 0-12.

[0065] 2. Preparation Methods of the Compounds of the Invention

[0066] The present invention also provides a method for preparing the aforementioned compound, comprising: reacting a compound represented by formula II with a compound represented by formula III in the absence of a solvent or in an organic solvent in the presence of copper powder;

[0067]

[0068] Wherein, R1', R2' and R3' are each independently a hydrogen atom or an arbitrary substituent, X is -Cl, -Br or -I; and n is 0-50.

[0069] According to the preparation method of the present invention, the reaction is shown in the following figure:

[0070]

[0071] According to the preparation method of the present invention, in the compound represented by formula III, n is preferably 0-30, more preferably 0-16, and further preferably 0-12.

[0072] According to the preparation method of the present invention, the compound represented by Formula II only needs to have the above basic structure, and there are no particular restrictions on the types and quantities of R1', R2', and R3'. The compounds represented by Formula II and Formula III can be obtained commercially or produced by any known method. Those skilled in the art can select suitable raw materials to produce the compounds of the present invention based on the teachings of the present invention and taking into account cost and practical needs.

[0073] According to the preparation method of the present invention, in the compound represented by formula II, R1', R2' and R3' are each independently a hydrogen atom or a hydrocarbon group; the hydrocarbon group may be an alkyl group, a chain alkyl group such as a methyl group, an ethyl group or a propyl group, or a cycloalkyl group; the hydrocarbon group may also be an aryl group such as a phenyl group.

[0074] According to the preparation method of the present invention, in the compound represented by formula II, the substituents on the benzene ring (marked as ①, ②, ③, ④) can be located at any position on the benzene ring, that is, at the ortho, meta or para position of the vinyl group; preferably, the substituent on the benzene ring ④ is located at the para position of the vinyl group; more preferably, all substituents on the benzene ring are located at the para position of the vinyl group.

[0075] According to the preparation method of the present invention, the amount of the compound of Formula III is determined relative to the amount of halogen atoms in the compound of Formula II. Generally, the compound of Formula III is used in excess, or even in a significant excess. Those skilled in the art can determine the appropriate ratio of the amounts of the compounds through simple experiments based on the teachings of the present invention and the actual needs of the reaction.

[0076] According to the preparation method of the present invention, one embodiment is: in the compound represented by formula II, R1', R2' and R3' are each independently a hydrogen atom or a hydrocarbon group, preferably R1', R2' and R3' are all hydrogen atoms; in the compound represented by formula III, n is preferably 4 to 12; the molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.01 to 1):(1 to 100), preferably 1:(0.03 to 0.5):(1.5 to 30).

[0077] According to the preparation method of the present invention, another embodiment is: in the compound represented by formula II, one of R1', R2' and R3' is the same as the substituent on the benzene ring ④ (preferably, the position on the benzene ring is also the same relative to the vinyl group), and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group; preferably, the remaining substituents are all hydrogen atoms; n is preferably 2 to 12; the molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.01 to 1):(2 to 100), preferably 1:(0.03 to 0.5):(3 to 30).

[0078] According to the preparation method of the present invention, another embodiment is: two of R1', R2' and R3' are the same as the substituents on the benzene ring ④ (preferably, the positions on the benzene ring relative to the vinyl group are also the same); the remaining substituents are hydrogen atoms or hydrocarbon groups, preferably the remaining substituents are hydrogen atoms; n is preferably 0 to 12; the molar ratio of the compound of formula II to the compound of formula III is generally the molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.01 to 1):(3 to 100), preferably 1:(0.03 to 0.5):(4 to 30).

[0079] According to the preparation method of the present invention, another embodiment is: in the compound represented by formula II, R1', R2' and R3' are the same as the substituents on the benzene ring ④ (preferably, the positions on the benzene ring relative to the vinyl group are also the same); n is preferably 0 to 12; the molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.01 to 1):(4 to 100), preferably 1:(0.03 to 0.5):(5 to 30).

[0080] In some embodiments, the compound represented by Formula II is 4-chlorotetraphenylethylene, 4-bromotetraphenylethylene, 4-iodotetraphenylethylene, di-(4-bromo)-tetraphenylethylene (cis or trans) or tetra-(4-bromo)-tetraphenylethylene.

[0081] In some embodiments, the compound represented by Formula III is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, and nonaethylenedecaamine.

[0082] According to the preparation method of the present invention, the reaction temperature is generally 80°C to 200°C.

[0083] According to the preparation method of the present invention, the reaction time is generally 2 hours to 168 hours.

[0084] According to the preparation method of the present invention, the reaction solvent may be 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

[0085] According to the preparation method of the present invention, the molar ratio of the compound of formula II, copper and the compound of formula III can be 1:(0.01-1):(1-100), preferably 1:(0.03-0.5):(1.5-30).

[0086] According to the preparation method of the present invention, after the reaction is completed, the clear liquid is separated and the solvent is removed to obtain the reaction product; alternatively, after the reaction is completed, water and an organic solvent are added for extraction, the organic phase is collected, and the organic solvent is removed to obtain the reaction product. Separation can be performed by centrifugation or filtration; the organic solvent used for extraction can be dichloromethane, chloroform, carbon tetrachloride, ether, or ethyl acetate; the organic solvent can be removed by any appropriate means, such as rotary evaporation; before removing the organic solvent, the organic phase can be dried, such as with a desiccant; the desiccant can be anhydrous sodium sulfate or anhydrous magnesium sulfate. The aforementioned reaction product can be further purified by column chromatography to obtain a purified reaction product.

[0087] The present invention also provides a product obtained by the aforementioned preparation method, comprising any of the aforementioned compounds. The product may be a reaction product obtained directly after removal of the organic solvent, or a reaction product obtained after further purification. The product may be used as a metal corrosion inhibition component.

[0088] 3. Application of the compounds of the present invention

[0089] The present invention provides the use of any of the aforementioned compounds or products prepared by any of the aforementioned methods in the field of metal hydrogen evolution corrosion protection.

[0090] According to the application of the present invention, any of the aforementioned compounds or products prepared by any of the aforementioned methods are suitable for environments where hydrogen evolution corrosion exists, and are particularly suitable for environments where hydrogen evolution corrosion is the main or only cause of corrosion.

[0091] According to the application of the present invention, any of the aforementioned compounds or products produced by any of the aforementioned methods are used as metal corrosion inhibitors in a strongly acidic environment. The strongly acidic environment can be an aqueous phase containing varying concentrations of strong acids, such as one or more of sulfuric acid, hydrochloric acid, mud acid, and aminosulfonic acid. The strongly acidic environment can have a pH of less than 3.

[0092] According to the application of the present invention, any of the aforementioned compounds or products produced by any of the aforementioned methods are used as metal corrosion inhibitors in a weakly acidic environment. The weakly acidic environment can be an aqueous phase containing varying concentrations of weak acids, such as one or more of formic acid, acetic acid, and citric acid, or one or more of dissolved CO2, H2S, SO2, etc. In the present invention, the weakly acidic environment can have a pH of 3 to 7.

[0093] The present invention provides a metal corrosion inhibitor, which contains any of the aforementioned compounds or a product prepared by any of the aforementioned methods.

[0094] The present invention also provides a metal corrosion inhibition method, wherein a corrosive medium contains any of the aforementioned compounds or a product produced by any of the aforementioned methods. The concentration of any of the aforementioned compounds in the corrosive medium can be controlled within a range of 40 mg / L to 160 mg / L, preferably 60 mg / L to 140 mg / L, and more preferably 70 mg / L to 120 mg / L.

[0095] The present invention also provides another metal corrosion inhibition method, wherein the corrosive medium contains any of the aforementioned compounds, and the total concentration of any of the aforementioned compounds in the corrosive medium is detected and controlled by ultraviolet-visible absorption spectroscopy; preferably, the total concentration of any of the aforementioned compounds in the corrosive medium is detected by ultraviolet-visible absorption spectroscopy and controlled to be within 40 mg / L to 160 mg / L.

[0096] The present invention also provides a copper corrosion protection method, wherein any of the aforementioned compounds is adsorbed on the copper surface, and the fluorescence of the copper surface under ultraviolet light is used to perform corrosion inhibition treatment on areas of the copper surface that have no fluorescence or have weaker fluorescence than other areas.

[0097] According to the copper corrosion protection method of the present invention, the corrosion inhibition treatment is to supplement the adsorption of any of the aforementioned compounds.

[0098] The copper corrosion protection method of the present invention allows for targeted corrosion protection by simply adding corrosion inhibitor and repairing the protective film in areas where no corrosion inhibitor has been absorbed, no protective film has formed, or where the corrosion inhibitor has desorbed and the protective film is incomplete. This method saves reagents while providing efficient protection, thus achieving targeted corrosion protection. This can be easily implemented on flat metal surfaces, and even on the inner walls of metal pipes, with the aid of an endoscopic UV light source and dosing equipment, detection and targeted dosing can be achieved.

[0099] The present invention 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 invention, but are not intended to limit the present invention in any form.

[0100] Instruments and Tests

[0101] In the examples, nuclear magnetic resonance analysis (1H NMR) was performed using a Bruker Avance 400 MHz nuclear magnetic resonance spectrometer; mass spectrometry (TOF-MS) was performed using a Bruker Autoflex III-MALDI-TOF-MS time-of-flight mass spectrometer; and UV-visible absorption spectroscopy was performed using a Perkin Elmer Lambda 750 UV spectrophotometer.

[0102] Example 1

[0103] This example is used to illustrate the preparation of the compound of the present invention.

[0104] The preparation method is shown in the figure below.

[0105]

[0106] The specific steps are as follows: 1.234 g of 4-bromotetraphenylethylene (3 mmol), 2 mg of copper powder (0.03 mmol), 0.181 g of ethylenediamine (3 mmol), and 3 mL of 1,4-dioxane are added to a test tube. The mixture is heated to 80°C with magnetic stirring and reacted for 2 hours. The mixture is cooled to room temperature, and appropriate amounts of dichloromethane and water are added for separation and extraction. This process is repeated three times. The organic phase is collected, dried, filtered, and spin-dried. The mixture is then purified by column chromatography to obtain 0.427 g of a yellow solid, which is the target product.

[0107] 1H NMR (400MHz, DMSO): δ7.25-6.90 (15H, m), 6.73-6.63 (2H, d), 6.40-6.30 (2H, d), 3.18-3.08 (2H, t), 2.72-2.62 (2H, t).

[0108] MS (TOF-MS): [M+Na + ]413.126.

[0109] Example 2

[0110] This example is used to illustrate the preparation of the compound of the present invention.

[0111] The preparation method is shown in the figure below.

[0112]

[0113] The specific steps are as follows: 1.234 g of 4-bromotetraphenylethylene (3 mmol), 19.2 mg of copper powder (0.3 mmol), and 5.679 g of tetraethylenepentamine (30 mmol) are added to a test tube. The mixture is heated to 100°C with magnetic stirring and reacted for 24 hours. The mixture is cooled to room temperature, and appropriate amounts of dichloromethane and water are added for separation and extraction. This process is repeated three times. The organic phase is collected, dried, filtered, and spin-dried. The organic phase is then purified by column chromatography to obtain 1.125 g of the desired product as a yellow, viscous liquid.

[0114] 1H NMR (400MHz, DMSO): δ7.25-6.90 (15H, m), 6.75-6.65 (2H, d), 6.43-6.33 (2H, d), 3.20-3.10 (2H, m), 2.74-2.64 (6H, m), 2.58-2.52 (8H, m).

[0115] MS (TOF-MS): [M+Na + ]542.261,[M+K + ]558.251.

[0116] Example 3

[0117] This example is used to illustrate the preparation of the compound of the present invention.

[0118] The preparation method is shown in the figure below.

[0119]

[0120] The specific steps are as follows: 1.234 g of 4-bromotetraphenylethylene (3 mmol), 96 mg of copper powder (1.5 mmol), and 6.971 g of pentaethylenehexamine (30 mmol) are added to a test tube. The mixture is heated to 140°C with magnetic stirring and reacted for 72 hours. The mixture is cooled to room temperature, and appropriate amounts of dichloromethane and water are added. Separate extraction is repeated three times. The organic phase is collected, dried, filtered, and spin-dried. The organic phase is then purified by column chromatography to obtain 1.175 g of the desired product as a yellow, viscous liquid.

[0121] Example 4

[0122] This example is used to illustrate the preparation of the compound of the present invention.

[0123] The preparation method is shown in the figure below.

[0124]

[0125] The specific steps are as follows: 1.471 g of di-(4-bromo)-tetraphenylethylene (3 mmol), 128 mg of copper powder (2 mmol), and 5.679 g of tetraethylenepentamine (30 mmol) are added to a test tube. The mixture is heated to 160°C with magnetic stirring and reacted for 72 hours. The mixture is cooled to room temperature, and appropriate amounts of dichloromethane and water are added. Separate extraction is repeated three times. The organic phase is collected, dried, filtered, and spin-dried. The organic phase is then purified by column chromatography to obtain 1.378 g of the target product as a yellow viscous liquid.

[0126] Example 5

[0127] This example is used to illustrate the preparation of the compound of the present invention.

[0128] The preparation method is shown in the figure below.

[0129]

[0130] The specific steps are as follows: 1.944 g of tetrakis-(4-bromo)tetraphenylethylene (3 mmol), 192 mg of copper powder (3 mmol), and 56.79 g of tetraethylenepentamine (300 mmol) are added to a test tube. The mixture is heated to 200°C with magnetic stirring and reacted for 168 hours. The mixture is cooled to room temperature, and appropriate amounts of dichloromethane and water are added. Separate extraction is repeated three times. The organic phase is collected, dried, filtered, and spin-dried. The mixture is then purified by column chromatography to obtain 1.792 g of the desired product as a yellow viscous liquid.

[0131] Example 6

[0132] This example is used to illustrate the rotating coupon corrosion test.

[0133] Prepare the corrosion solution: Dissolve 208g of concentrated H2SO4 in 4L of deionized water to make a 0.5M H2SO4 solution. Then, take 250mL of the 0.5M H2SO4 solution and place 250mL of the 0.5M H2SO4 solution in different glass bottles. Hang metal test pieces that have been treated with ethanol and weighed in these glass bottles in order, immersing the test pieces in the solution without touching the bottom or walls of the bottles. One bottle is left untreated as a blank test (i.e., Comparative Example 1). A certain concentration of the corrosion inhibition component products prepared in the previous examples (i.e., Examples 1 to 5) and a certain concentration of the halogenated tetraphenylethylene and polyethylene polyamine raw materials in the previous examples (i.e., Comparative Examples 2 to 5) are added. The glass bottles containing the corrosion solution and test pieces are placed in a rotary sheet tester set to a temperature of 60°C, a rotation speed of 28 rpm, and a linear speed of 1 m / s. After a certain period of time, the test pieces are removed and treated with water, ethanol, etc., and then weighed. The mass loss of the test pieces before and after the test is calculated to determine the corrosion inhibition performance of the agent.

[0134] The corrosion inhibition rate calculation formula is as follows:

[0135] η=(Δm0-Δm1) / Δm0×100

[0136] Where: η——corrosion inhibition rate, %

[0137] Δm0——mass loss of the test piece in the blank test, g

[0138] Δm1——mass loss of the test piece during the dosing test, g

[0139] Rotating coupon corrosion tests were conducted using the same method on H62 brass and N80 carbon steel specimens, with the exception of the test durations of 72 hours for brass and 4 hours for carbon steel. The results for the brass specimens are shown in Table 1, and the results for the carbon steel specimens are shown in Table 2.

[0140] The results in Table 1 show that for brass, the corrosion inhibition rate of the corrosion-inhibiting component of the present invention gradually increases with increasing agent concentration. When the agent concentration is 100 mg / L, the corrosion inhibition rates of Examples 1 to 5 all exceed 75%, with Examples 4 and 5 achieving inhibition rates exceeding 99%, demonstrating excellent corrosion inhibition performance. However, the corrosion inhibition performance of the halogenated tetraphenylethylene and polyethylene polyamine raw materials, i.e., Comparative Examples 2 to 5, is poor, with inhibition rates below 25% at 100 mg / L.

[0141] The results in Table 2 show that for carbon steel, the corrosion inhibition rate of the corrosion-inhibiting component of the present invention gradually increases with increasing agent concentration. When the agent concentration is 100 mg / L, the corrosion inhibition rates of Examples 1 to 5 all exceed 75%, and the corrosion inhibition rates of Examples 2 to 5 exceed 95%, indicating excellent corrosion inhibition performance. However, the corrosion inhibition performance of the halogenated tetraphenylethylene and polyethylene polyamine raw materials, namely Comparative Examples 2 to 5, is poor, with corrosion inhibition rates below 25% at 100 mg / L.

[0142] Table 1

[0143] Drug concentration 40mg / L 70mg / L 100mg / L Comparative Example 1: Blank Test - - - Comparative Example 2: Bromotetraphenylethylene -8.3％ -1.6％ 2.9％ Comparative Example 3: Di-(4-bromo)-tetraphenylethylene -5.6％ 7.2％ 1.5％ Comparative Example 4: Ethylenediamine 6.2％ 11.3％ 15.9％ Comparative Example 5: Tetraethylenepentamine 11.6％ 17.2％ 23.5％ Example 1 51.0％ 64.4％ 78.8％ Example 2 69.5％ 84.1％ 89.2％ Example 3 76.9％ 87.5％ 94.9％ Example 4 92.2％ 95.8％ 99.1％ Example 5 95.3％ 97.2％ 99.4％

[0144] Table 2

[0145] Drug concentration 40mg / L 70mg / L 100mg / L Comparative Example 1: Blank Test - - - Comparative Example 2: Bromotetraphenylethylene -5.5％ 3.5％ 0.6％ Comparative Example 3: Di-(4-bromo)-tetraphenylethylene -8.7％ -5.0％ 7.2％ Comparative Example 4: Ethylenediamine 4.6％ 8.0％ 12.8％ Comparative Example 5: Tetraethylenepentamine 7.2％ 12.7％ 18.3％ Example 1 50.5％ 66.2％ 79.3％ Example 2 70.8％ 89.0％ 96.1％ Example 3 78.2％ 90.9％ 96.6％ Example 4 91.9％ 93.8％ 97.3％ Example 5 93.2％ 95.9％ 98.1％

[0146] Example 7

[0147] This example is used to illustrate the concentration determination of the compound of the present invention in a corrosive medium. Taking the product of Example 1 as an example, it was prepared into solutions of different mass concentrations using 0.5M H2SO4 as a solvent and subjected to UV-visible absorption spectrum measurement. Figure 5As can be seen, this compound has a distinct UV absorption peak. A linear fit of the absorbance Abs at the 307nm peak and the mass concentration c yields the relationship Abs = 0.02119c - 0.02493. When the corrosive medium contains an unknown concentration of this compound, the UV-Vis absorption spectrum of the solution can be measured to obtain the absorbance at 307nm. Substituting this into the above relationship yields the mass concentration of the compound in the corrosive medium. If the concentration is too high and the absorbance exceeds the measuring range, the sample should be diluted appropriately before measurement.

[0148] Example 8

[0149] This example is used to illustrate the fluorescence of the compound of the present invention adsorbed on the copper surface.

[0150] After the corrosion test of the brass test piece in Example 6 was completed, the corrosion inhibition component product was adsorbed on the surface of the test pieces of Examples 1 to 5, and the test pieces showed a certain intensity of fluorescence under 365nm ultraviolet light; the test piece without adding any agent (Comparative Example 1) had no fluorescence under 365nm ultraviolet light; the test pieces containing halogenated tetraphenylethylene and polyethylene polyamine raw materials with almost no corrosion inhibition performance (Comparative Examples 2 to Comparative Examples 5) had no fluorescence under 365nm ultraviolet light. Figure 6 From left to right, the photographs of the test pieces of Comparative Example 1, 100 mg / L Comparative Example 2, 100 mg / L Comparative Example 3, 100 mg / L Comparative Example 4, 100 mg / L Comparative Example 5, 100 mg / L Example 1, 100 mg / L Example 2, 100 mg / L Example 3, 100 mg / L Example 4, and 100 mg / L Example 5 after the corrosion test under 365 nm ultraviolet light are shown. It can be seen that the corrosion inhibition component of the present invention has a visual detection effect.

Claims

1. A compound, characterized in that It has the structure shown in formula I: wherein n is 0 to 16; R1, R2 and R3 are each independently a hydrogen atom or the same as the substituent on the benzene ring ④.

2. The compound according to claim 1, characterized in that The substituents on the benzene ring are all located in the para position relative to the vinyl group.

3. The compound according to claim 1, characterized in that R1, R2 and R3 are hydrogen atoms; n is 4 to 12.

4. The compound according to claim 1, characterized in that One of R1, R2 and R3 is the same as the substituent on the benzene ring ④, and the remaining substituents are hydrogen atoms; n is 2 to 12.

5. The compound according to claim 1, characterized in that Two of R1, R2 and R3 are the same as the substituents on the benzene ring ④; the remaining substituents are hydrogen atoms; and n is 0 to 12.

6. The compound according to claim 1, characterized in that R1, R2 and R3 are the same as the substituents on the benzene ring ④; n is 0 to 12.

7. A method for preparing the compound of claim 1, comprising: reacting the compound represented by formula II with the compound represented by formula III in the presence of copper powder in the absence of solvent or in an organic solvent; wherein R1′, R2′ and R3′ are each independently a hydrogen atom or X, X is —Cl, —Br or —I; and n is 0-16.

8. The preparation method according to claim 7, characterized in that: In the compound represented by formula II, the substituents on the benzene ring are all located in the para position relative to the vinyl group.

9. The preparation method according to claim 7, characterized in that: The reaction temperature is 80°C to 200°C.

10. The preparation method according to claim 7, characterized in that: The reaction time is 2h~168h.

11. The preparation method according to claim 7, characterized in that: The molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.01-1):(1-100).

12. The preparation method according to claim 11, characterized in that: The molar ratio of the compound of formula II, copper and the compound of formula III is 1:(0.03-0.5):(1.5-30).

13. The preparation method according to claim 7, characterized in that: The reaction solvent is 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

14. A metal corrosion inhibition component, characterized in that Prepared by the method of any one of claims 7 to 13.

15. Use of any compound according to claim 1 to 6 or the metal corrosion inhibition component according to claim 14 in the field of metal hydrogen evolution corrosion protection.

16. A metal corrosion inhibitor, characterized in that Containing any one of the compounds of claims 1 to 6 or the metal corrosion inhibition component of claim 14.

17. A metal corrosion inhibition method, characterized in that: The corrosive medium contains any one of the compounds of claims 1 to 6 or the metal corrosion inhibition component of claim 14.

18. A metal corrosion inhibition method, characterized in that: The corrosive medium contains any one of the compounds according to claims 1 to 6, and the concentration of the compound in the corrosive medium is detected and controlled by ultraviolet-visible absorption spectroscopy.

19. The metal corrosion inhibition method according to claim 18, characterized in that: The concentration of the compound in the corrosive medium is controlled within a range of 40 mg / L to 160 mg / L.

20. A copper corrosion protection method, characterized in that: The copper surface is adsorbed with any one of the compounds of claims 1 to 6, and the fluorescence of the copper surface under ultraviolet light is used to perform corrosion inhibition treatment on areas of the copper surface that have no fluorescence or have weaker fluorescence than other areas.

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