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 ethylene glycol or polyethylene glycol group to a tetraphenylethylene group. The compound not only exhibits excellent metal corrosion inhibition properties but also easily detects its concentration in corrosive media. Furthermore, upon adsorption onto a metal surface, the compound emits strong fluorescence, enabling visual detection.

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, acetylene alcohols, benzotriazoles, 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 new corrosion inhibitors with better performance. 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] The first object of the present invention is to provide a compound and a preparation method thereof, wherein the compound has excellent metal corrosion inhibition function and is a new type of metal corrosion inhibition component. The second object of the present invention is to provide a metal corrosion inhibition method using the compound as the corrosion inhibition component, which has excellent corrosion inhibition effect on carbon steel, brass, etc. 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 performed more conveniently and timely. The fourth object of the present invention is to provide a method for positioning corrosion protection, which utilizes the fluorescence effect of the metal corrosion inhibition component adsorbed on the metal surface to promptly discover corrosion hazards and perform fixed-point and positioned corrosion protection, thereby effectively preventing or reducing 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; R1, R2, R3 and R4 are each independently a hydrogen atom or any substituent.

[0010] 2. The compound according to 1, wherein n is 1 to 30, preferably 2 to 16, and more preferably 3 to 12.

[0011] 3. A compound according to any of the preceding claims, wherein R4 is a hydrogen atom, a hydrocarbon group or the same as another substituent on the nitrogen atom in the structure of formula I.

[0012] 4. A compound according to any of the preceding claims, characterized in that R1, R2 and R3 are each independently a hydrogen atom, a hydroxyl group, an amino group, a mercapto group, a hydrocarbon group or the same as the substituent on the benzene ring ④.

[0013] 5. A compound according to any of the preceding claims, wherein the substituents on the benzene ring are all located in the para position relative to the vinyl group.

[0014] 6. A compound according to any of the preceding claims, wherein R1, R2, R3 and R4 are each independently a hydrogen atom or a hydrocarbon group, preferably R1, R2, R3 and R4 are all hydrogen atoms; n is preferably 4 to 12; or

[0015] R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group, preferably R1, R2 and R3 are all hydrogen atoms; R4 is the same as another substituent on the nitrogen atom in the structure shown in Formula I; n is preferably 2 to 9; or

[0016] One of R1, R2 and R3 is the same as the substituent on the benzene ring ④, and the remaining substituents and R4 are each independently a hydrogen atom or a hydrocarbon group, preferably the remaining substituents and R4 are all hydrogen atoms; n is preferably 2 to 12; or

[0017] Two of R1, R2 and R3 are the same as the substituents on the benzene ring ④; the remaining substituents and R4 are each independently a hydrogen atom or a hydrocarbon group, preferably the remaining substituents and R4 are all hydrogen atoms; n is preferably 1 to 12;

[0018] R1, R2 and R3 are the same as the substituents on the benzene ring ④; R4 is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom; and n is preferably 0 to 12.

[0019] 7. A method for preparing a compound, comprising: reacting a compound represented by formula II with a compound represented by formula III in the presence of a base,

[0020]

[0021] Wherein, R1', R2', R3' and R4' are each independently a hydrogen atom or any substituent; n is 0 to 50, and X is -Cl, -Br, -I, -OSO2CH3, -OSO2C6H5 or -OSO2C6H5CH3.

[0022] 8. A method according to any of the above, characterized in that n is 1 to 30, preferably 2 to 16, and more preferably 3 to 12.

[0023] 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.

[0024] 10. A preparation method according to any of the foregoing, characterized in that, in the compound represented by 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, a hydroxyl group, a thiol group 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 atom, a hydroxyl group, a thiol group or a hydrocarbon group; or all of R1', R2' and R3' are the same as the substituent on the benzene ring ④.

[0025] 11. A method according to any of the preceding claims, characterized in that the base is Na2CO3, K2CO3, Cs2CO3, NaOH, KOH, CsOH, NaOCH3, NaOC2H5, KOCH3, KOC2H5, LiH, NaH, KH or CaH2.

[0026] 12. A method according to any of the preceding claims, characterized in that the reaction temperature is 60°C to 150°C.

[0027] 13. A preparation method according to any of the above, characterized in that the reaction time is 2h to 168h.

[0028] 14. A preparation method according to any of the above, characterized in that the reaction solvent is tetrahydrofuran, 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide or dimethyl sulfoxide.

[0029] 15. A metal corrosion inhibition component, characterized in that it is prepared by any of the above methods.

[0030] 16. Use of any of the aforementioned compounds or the metal corrosion inhibition component of 15 in protecting metals from hydrogen evolution corrosion.

[0031] 17. A metal corrosion inhibitor, characterized by containing any of the aforementioned compounds or the metal corrosion inhibition component of 15.

[0032] 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.

[0033] 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.

[0034] 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.

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

[0036] 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 new type of high-efficiency metal corrosion inhibition component.

[0037] 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.

[0038] 3. Even if the compound of the present invention is adsorbed and accumulated on the metal surface, it can 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.

[0039] Other features and advantages of the present invention will be described in detail in the detailed description section. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product in Example 1.

[0041] Figure 2 This is the mass spectrum of the product of Example 1.

[0042] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the product in Example 2.

[0043] Figure 4 This is the mass spectrum of the product of Example 2.

[0044] Figure 5 This is the UV-visible absorption spectrum of the product in Example 1.

[0045] Figure 6 This is a photo of the brass specimen under ultraviolet light after the corrosion test. DETAILED DESCRIPTION

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] In the present invention, the ethylene glycol group refers to -CH2CH2OH.

[0051] In the present invention, polyethylene glycol group refers to -(CH2CH2O) m H,m>1.

[0052] In the present invention, the corrosive medium refers to an acidic medium containing water or consisting essentially of water.

[0053] 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.

[0054] 1. Compounds of the Present Invention

[0055] The present invention provides a compound having the structure shown in Formula I:

[0056]

[0057] wherein n is 0 to 50; R1, R2, R3 and R4 are each independently a hydrogen atom or any substituent.

[0058] According to the present invention, it has been found that the structure of "a nitrogen atom connecting an ethylene glycol group or a polyethylene glycol group to a tetraphenylethylene group" makes the compound easily adsorbed on a metal surface and has excellent metal corrosion inhibition performance, becoming a new type of metal corrosion inhibition component. According to the compound of the present invention, the above basic structure enables the compound to have excellent metal corrosion inhibition performance, and therefore there is no particular limitation on the type and quantity of R1, R2, R3 and R4. Those skilled in the art can select suitable raw materials to manufacture the compound of the present invention based on the teachings of the present invention and considering cost and practical needs.

[0059] 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. Generally, fluorescence quenching occurs when fluorescent substances are adsorbed on metal surfaces; fluorescent substances generally 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 can save reagents and provide efficient protection, thereby achieving localized corrosion protection.

[0060] According to the compound of the present invention, n is preferably 1-30, more preferably 2-16, and even more preferably 3-12.

[0061] According to the compounds of the present invention, R1, R2 and R3 are each independently a hydrogen atom (-H), a hydroxyl group (-OH), an amino group (-NH2), a mercapto group (-SH), a hydrocarbon group or the same as the substituent on the benzene ring ④; 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, and the hydrocarbon group may also be an aromatic group such as a phenyl group.

[0062] According to the compounds of the present invention, R4 is a hydrogen atom, a hydrocarbon group, or the same as another substituent on the nitrogen atom in the structure represented by Formula I. 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.

[0063] 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.

[0064] According to the compound of the present invention, one embodiment is: R1, R2, R3 and R4 are each independently a hydrogen atom or a hydrocarbon group, preferably R1, R2, R3 and R4 are all hydrogen atoms; and n is preferably 4-12.

[0065] According to the compound of the present invention, another embodiment is: R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group, preferably R1, R2 and R3 are all hydrogen atoms; R4 is the same as another substituent on the nitrogen atom in the structure shown in Formula I; and n is preferably 2 to 9.

[0066] 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 and R4 are each independently a hydrogen atom or a hydrocarbon group; preferably, "the remaining substituents and R4" are all hydrogen atoms; n is preferably 2 to 12.

[0067] 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 relative to the vinyl group are also the same); the remaining substituents and R4 are each independently a hydrogen atom or a hydrocarbon group, more preferably "the remaining substituents and R4" are all hydrogen atoms; n is preferably 1 to 12.

[0068] According to the compound of the present invention, another embodiment is: 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), R4 is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom; n is preferably 0 to 12.

[0069] 2. Preparation Methods of the Compounds of the Invention

[0070] The present invention also provides a method for preparing the aforementioned compound, comprising: reacting the compound represented by formula II with the compound represented by formula III in the presence of a base,

[0071]

[0072] wherein R1', R2', R3' and R4' are each independently a hydrogen atom or any substituent; n is 0 to 50, and X is -Cl, -Br, -I, methanesulfonate (-OSO2CH3), benzenesulfonate (-OSO2C6H5) or p-toluenesulfonate (-OSO2C6H5CH3).

[0073] According to the preparation method of the present invention, the reaction is as follows:

[0074]

[0075] According to the preparation method of the present invention, in the compound represented by formula III, n is preferably 1-30, more preferably 2-16, and even more preferably 3-12.

[0076] 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 is no particular limitation on the type and quantity of R1', R2', R3', and R4'. 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.

[0077] According to the preparation method of the present invention, in the compound represented by Formula II, R4' can be a hydrogen atom or a hydrocarbon group; the hydrocarbon group can be an alkyl group, a chain alkyl group such as a methyl, ethyl, or propyl group, or a cycloalkyl group, or an aryl group such as a phenyl group. The hydrocarbon group can be alkylated with an alkylating agent using any known method to attach the amino group on the benzene ring to the nitrogen atom. This is common knowledge in organic synthesis and will not be elaborated upon in the present invention.

[0078] 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 (-H), a hydroxyl group (-OH), a mercapto group (-SH), a hydrocarbon group or the same as the substituent on the benzene ring ④; 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, and the hydrocarbon group may also be an aromatic group such as a phenyl group.

[0079] 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.

[0080] According to the preparation method of the present invention, the amount of the compound of formula III is determined relative to the amount of the amino group in the compound of formula II. Those skilled in the art can determine the appropriate ratio of the amounts of the substances through simple experiments according to actual needs.

[0081] 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; R4' is a hydrogen atom or a hydrocarbon group; in the compound represented by formula III, n is preferably 4 to 12; the molar ratio of the compound of formula II to the compound of formula III is generally 1:(0.5 to 1.5), preferably 1:(0.8 to 1.2), and more preferably 1:(0.9 to 1.1).

[0082] According to the preparation method of the present invention, another 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; R4' is a hydrogen atom; in the compound represented by formula III, n is preferably 2 to 9; the molar ratio of the compound of formula II to the compound of formula III is generally 1:(1.5 to 10), preferably 1:(2 to 5).

[0083] 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 and R4' are each independently a hydrogen atom or a hydrocarbon group; preferably, "the remaining substituents and R4" are all hydrogen atoms; n is preferably 2 to 12; the molar ratio of the compound of formula II to the compound of formula III is generally 1:(1.5 to 20), preferably 1:(2 to 10).

[0084] 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 and R4' are each independently a hydrogen atom or a hydrocarbon group, preferably the remaining substituents and R4' are all hydrogen atoms; n is preferably 1 to 12; the molar ratio of the compound of formula II to the compound of formula III is generally 1:(2 to 30), preferably 1:(3 to 15).

[0085] 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 are also the same relative to the vinyl group), R4' is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom; n is preferably 0 to 12; the molar ratio of the compound of formula II to the compound of formula III is generally 1:(3 to 40), preferably 1:(4 to 20).

[0086] In some embodiments, the compound represented by Formula II is 4-aminotetraphenylethylene, di-4-aminotetraphenylethylene (cis or trans), tetra-4-aminotetraphenylethylene or 4-(N-methyl)amino-tetraphenylethylene.

[0087] In some embodiments, the compound represented by Formula III is a halogenated triethylene glycol, a halogenated tetraethylene glycol, a halogenated hexaethylene glycol, a tetraethylene glycol methanesulfonate, or a decaethylene glycol p-toluenesulfonate; wherein the halogen atom can be chlorine, bromine, or iodine (-Cl, -Br, or -I).

[0088] According to the preparation method of the present invention, the base can be Na2CO3, K2CO3, Cs2CO3, NaOH, KOH, CsOH, NaOCH3, NaOC2H5, KOCH3, KOC2H5, LiH, NaH, KH or CaH2.

[0089] According to the preparation method of the present invention, the reaction temperature is generally 60°C to 150°C.

[0090] According to the preparation method of the present invention, the reaction time is generally 2 hours to 168 hours.

[0091] According to the preparation method of the present invention, the reaction solvent may be tetrahydrofuran, 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide or dimethyl sulfoxide.

[0092] According to the preparation method of the present invention, after the reaction is completed, the reaction is quenched, extracted with an organic solvent, and the organic phase is collected. After removing the organic solvent, the reaction product can be obtained. The reaction can be quenched with water after the reaction is completed. The organic solvent used for extraction can be dichloromethane, chloroform, carbon tetrachloride, ether, or ethyl acetate. The organic solvent can be removed by any suitable 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 reaction product can be further purified by column chromatography to obtain a purified reaction product.

[0093] 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.

[0094] 3. Application of the compounds of the present invention

[0095] The present invention provides the use of any of the aforementioned compounds or products prepared by any of the aforementioned methods in protecting metals from hydrogen evolution corrosion.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] Instruments and Tests

[0107] In the examples, nuclear magnetic resonance analysis (1H NMR) was performed using a Bruker Avance 400 MHz nuclear magnetic resonance spectrometer; mass spectrometry analysis (ESI-MS) was performed using a Bruker Solarix FT-ICR MS Fourier transform ion cyclotron resonance mass spectrometer; and UV-visible absorption spectroscopy analysis was performed using a Perkin Elmer Lambda 750 UV spectrophotometer.

[0108] Example 1

[0109] This example is used to illustrate the preparation of the compound of the present invention.

[0110] The preparation method is shown in the following formula.

[0111]

[0112] The specific steps are as follows: add 25mL of tetrahydrofuran and 1.738g of 4-aminotetraphenylethylene (5mmol) to a 100mL three-necked flask, stir and dissolve, and protect with N2. Add 0.967g of K2CO3 (7mmol) and react for 30 minutes. Then dissolve 0.843g of chlorotriethylene glycol (5mmol) in 5mL of tetrahydrofuran and slowly add dropwise to the reaction system. Heat to 70°C and react for 3 hours. Then cool to room temperature, add appropriate amounts of dichloromethane and water, and perform separation extraction. Repeat three times. Collect the organic phase, dry, spin dry, and purify by column chromatography to obtain 1.907g of a yellow viscous liquid, which is the target product.

[0113] 1H NMR (400MHz, DMSO): δ7.20-6.85 (15H, m), 6.70-6.60 (2H, d), 6.40-6.30 (2H, d), 3.55-3.37 (10H, m), 3.15-3.05 (2H, m).

[0114] MS (ESI-MS): [M+H + ]480.25366, [M+Na + ]502.23556.

[0115] Example 2

[0116] This example is used to illustrate the preparation of the compound of the present invention.

[0117] The preparation method is shown in the following formula.

[0118]

[0119] The specific steps are as follows: add 25mL 1,4-dioxane and 1.738g 4-aminotetraphenylethylene (5mmol) to a 100mL three-necked flask, stir and dissolve, and protect with N2. Add 0.560g NaOH (14mmol) and react for 30min. Then dissolve 3.085g bromotetraethylene glycol (12mmol) in 10mL dioxane and slowly add dropwise to the reaction system. Heat to 100℃ and react for 24h. Then cool to room temperature, add appropriate amount of dichloromethane and water, separate and extract, repeat three times, collect the organic phase, dry, spin dry, and purify by column chromatography to obtain 2.387g yellow viscous liquid, which is the target product.

[0120] 1H NMR (400MHz, DMSO): δ7.20-6.85 (15H, m), 6.80-6.70 (2H, d), 6.55-6.45 (2H, d), 3.83-3.73 (4H, t), 3.55-3.35 (24H, m), 3.15-3.05 (4H, t).

[0121] MS (ESI-MS): [M+H + ]700.3900.

[0122] Example 3

[0123] This example is used to illustrate the preparation of the compound of the present invention.

[0124] The preparation method is shown in the following formula.

[0125]

[0126] The specific steps are as follows: add 25mL N,N'-dimethylformamide and 1.812g di-4-aminotetraphenylethylene (5mmol) to a 100mL three-necked flask, stir and dissolve, and protect with N2. Add 0.336g NaH (14mmol) and react for 30min. Then dissolve 4.707g iodine hexaethylene glycol (12mmol) in 10mL N,N'-dimethylformamide and slowly add it dropwise to the reaction system. Heat to 120℃ and react for 48h. Then cool to room temperature, add appropriate amount of dichloromethane and water, separate and extract, repeat three times, collect the organic phase, dry, spin dry, and purify by column chromatography to obtain 2.712g yellow viscous liquid, which is the target product.

[0127] Example 4

[0128] This example is used to illustrate the preparation of the compound of the present invention.

[0129] The preparation method is shown in the following formula.

[0130]

[0131] The specific steps are as follows: add 25mL N,N'-dimethylacetamide and 1.963g tetra-4-aminotetraphenylethylene (5mmol) to a 100mL three-necked flask, stir and dissolve, and protect with N2. Add 0.672g NaH (28mmol) and react for 30min. Then dissolve 6.535g tetraethylene glycol methanesulfonate (24mmol) in 10mL N,N'-dimethylacetamide and slowly add dropwise to the reaction system. Heat to 150℃ and react for 168h. Then cool to room temperature, add appropriate amount of dichloromethane and water, separate and extract, repeat three times, collect the organic phase, dry, spin dry, and purify by column chromatography to obtain 3.016g of yellow viscous liquid, which is the target product.

[0132] Example 5

[0133] This example is used to illustrate the preparation of the compound of the present invention.

[0134] The preparation method is shown in the following formula.

[0135]

[0136] The specific steps are as follows: add 25mL dimethyl sulfoxide and 1.807g 4-(N-methyl)amino-tetraphenylethylene (5mmol) to a 100mL three-necked flask, stir and dissolve, and protect with N2. Add 0.476g NaOC2H5 (7mmol) and react for 30min. Then dissolve 3.064g decaethylene glycol p-toluenesulfonate (5mmol) in 10mL dimethyl sulfoxide and slowly add dropwise to the reaction system. Heat to 100℃ and react for 24h. Then cool to room temperature, add appropriate amount of dichloromethane and water, separate and extract, repeat three times, collect the organic phase, dry, spin dry, and purify by column chromatography to obtain 2.502g of yellow viscous liquid, which is the target product.

[0137] Example 6

[0138] This example is used to illustrate the rotating coupon corrosion test.

[0139] 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 into different glass bottles. Hang the metal test pieces treated with ethanol and weighed in these glass bottles in order, and immerse the test pieces in the solution without touching the bottom and wall of the bottle. One bottle does not add any reagent as a blank test (i.e., Comparative Example 0). Add a certain concentration of the corrosion inhibition component products prepared in the above examples (i.e., Examples 1 to 5) and a certain concentration of the aminotetraphenylethylene raw material in the above examples (i.e., Comparative Examples 1 to 3). Place the glass bottles containing the corrosion solution and test pieces in a rotary hanging instrument. Set the rotary hanging instrument temperature to 60°C, the speed to 28r / min, and the linear speed to 1m / s. After a certain period of time, the test piece is removed and weighed after being treated with water, ethanol, etc. The mass loss of the test piece before and after the test is calculated to obtain the corrosion inhibition performance of the agent.

[0140] The corrosion inhibition rate calculation formula is as follows:

[0141] η=(Δm0-Δm1) / Δm0×100

[0142] Where: η——corrosion inhibition rate, %

[0143] Δm0——mass loss of the test piece in the blank test, g

[0144] Δm1——mass loss of the test piece during the dosing test, g

[0145] 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.

[0146] 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 80%, with Examples 3 and 4 achieving inhibition rates exceeding 99%, demonstrating excellent corrosion inhibition performance. However, the aminotetraphenylethylene raw materials used in Comparative Examples 1 to 3 exhibit almost no corrosion inhibition performance.

[0147] 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. At an agent concentration of 100 mg / L, the corrosion inhibition rates of Examples 1 to 5 all exceeded 95%, demonstrating excellent corrosion inhibition performance. However, the aminotetraphenylethylene raw materials used in Comparative Examples 1 to 3 exhibited virtually no corrosion inhibition performance.

[0148] Table 1

[0149] Drug concentration 40mg / L 70mg / L 100mg / L Comparative Example 0 - - - Example 1 58.6％ 76.8％ 82.8％ Example 2 73.7％ 86.5％ 93.2％ Example 3 92.7％ 96.0％ 99.2％ Example 4 95.3％ 97.8％ 99.8％ Example 5 75.8％ 87.3％ 94.6％ Comparative Example 1: 4-aminotetraphenylethylene 2.5％ 7.7％ 5.2％ Comparative Example 2: Di-(4-amino)-tetraphenylethylene 0.3％ 17.8％ 10.8％ Comparative Example 3: Tetrakis-(4-amino)-tetraphenylethylene 1.1％ -2.1％ 8.3％

[0150] Table 2

[0151] Drug concentration 40mg / L 70mg / L 100mg / L Comparative Example 0 - - - Example 1 51.1％ 87.0％ 95.2％ Example 2 70.4％ 88.9％ 96.1％ Example 3 90.9％ 93.7％ 97.2％ Example 4 92.2％ 95.8％ 98.3％ Example 5 74.1％ 89.5％ 96.7％ Comparative Example 1: 4-aminotetraphenylethylene 3.3％ 6.8％ 6.1％ Comparative Example 2: Di-(4-amino)-tetraphenylethylene 1.7％ 11.2％ 8.3％ Comparative Example 3: Tetrakis-(4-amino)-tetraphenylethylene -2.5％ -0.9％ 5.2％

[0152] Example 7

[0153] 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 5 As can be seen, the compound has a distinct UV absorption peak. A linear fit of the absorbance Abs at the 300nm peak and the mass concentration c yields the relationship Abs = 0.02258c + 0.03224. When the corrosive medium contains an unknown concentration of the compound, the UV-Vis absorption spectrum of the solution can be measured to obtain the absorbance at 300nm. 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.

[0154] Example 8

[0155] This example is used to illustrate the fluorescence of the compound of the present invention adsorbed on the copper surface.

[0156] 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 0) had no fluorescence under 365nm ultraviolet light; the test pieces containing aminotetraphenylethylene raw materials with almost no corrosion inhibition performance (Comparative Examples 1 to Comparative Examples 3) had no fluorescence under 365nm ultraviolet light. Figure 6 From left to right, the photographs of the test pieces under 365nm UV light after the corrosion test are respectively Comparative Example 0, 100mg / L Example 1, 100mg / L Example 2, 100mg / L Example 3, 100mg / L Example 4, 100mg / L Example 5, 100mg / L Comparative Example 1, 100mg / L Comparative Example 2, and 100mg / L Comparative Example 3. 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 2 to 12; R1, R2, R3 and R4 are all hydrogen atoms; or R1, R2 and R3 are all hydrogen atoms; R4 is methyl, ethyl, propyl, phenyl or the same as another substituent on the nitrogen atom in the structure shown in Formula I; or One of R1, R2 and R3 is the same as the substituent on benzene ring ④, and the remaining substituents and R4 are hydrogen atoms; or Two of R1, R2 and R3 are the same as the substituents on the benzene ring ④; the remaining substituents and R4 are hydrogen atoms; or R1, R2 and R3 are the same as the substituents on the benzene ring ④, and R4 is a hydrogen atom.

2. A method for preparing the compound according to claim 1, comprising: In the presence of a base, the compound represented by formula II is reacted with the compound represented by formula III, wherein R1′, R2′, R3′ and R4′ are the same as R1, R2, R3 and R4, respectively; and X is —Cl, —Br, —I, —OSO2CH3, —OSO2C6H5 or —OSO2C6H5CH3.

3. The preparation method according to claim 2, 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.

4. The preparation method according to claim 2, characterized in that: The base is Na2CO3, K2CO3, Cs2CO3, NaOH, KOH, CsOH, NaOCH3, NaOC2H5, KOCH3, KOC2H5, LiH, NaH, KH or CaH2.

5. The preparation method according to claim 2, characterized in that: The reaction temperature is 60°C to 150°C.

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

7. The preparation method according to claim 2, characterized in that: The reaction solvent is tetrahydrofuran, 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide or dimethyl sulfoxide.

8. A metal corrosion inhibition component, characterized in that The active component is a compound prepared by the method according to any one of claims 2 to 7.

9. Use of the compound of claim 1 or the metal corrosion inhibition component of claim 8 in metal hydrogen evolution corrosion protection.

10. A metal corrosion inhibitor, characterized in that: Containing the compound of claim 1 or the metal corrosion inhibition component of claim 8.

11. A metal corrosion inhibition method, characterized in that: The corrosive medium contains the compound of claim 1 or the metal corrosion inhibition component of claim 8.

12. A metal corrosion inhibition method, characterized in that: The corrosive medium contains the compound of claim 1, and the concentration of the compound in the corrosive medium is detected and controlled by ultraviolet-visible absorption spectroscopy.

13. The metal corrosion inhibition method according to claim 12, 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.

14. A copper corrosion protection method, characterized in that: The compound of claim 1 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.

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