CN113801047B - Metal corrosion inhibitor and preparation method thereof - Google Patents

Metal corrosion inhibitor and preparation method thereof Download PDF

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Publication number
CN113801047B
CN113801047B CN202111182892.8A CN202111182892A CN113801047B CN 113801047 B CN113801047 B CN 113801047B CN 202111182892 A CN202111182892 A CN 202111182892A CN 113801047 B CN113801047 B CN 113801047B
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corrosion inhibitor
mixed solution
metal corrosion
metal
reaction
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CN113801047A (en
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游恒志
苏铭浩
卿晶
沈桂富
张颖鹤
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Shenzhen Zhonghe Headway Bio Sci & Tech Co ltd
Shenzhen Graduate School Harbin Institute of Technology
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Shenzhen Zhonghe Headway Bio Sci & Tech Co ltd
Shenzhen Graduate School Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/82—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/83—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
    • C07C323/59—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton with acylated amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/145—Amides; N-substituted amides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The application provides a metal corrosion inhibitor and a preparation method thereof, which relate to the technical field of metal materials, and the preparation method of the metal corrosion inhibitor comprises the following steps: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution; and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, obtaining a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor. The application can form coordination bond with metal atoms through metal corrosion inhibitor atoms, and form a compact monomolecular film layer on the metal surface to slow down the corrosion of metal.

Description

Metal corrosion inhibitor and preparation method thereof
Technical Field
The application relates to the technical field of metal materials, in particular to a metal corrosion inhibitor and a preparation method thereof.
Background
The metal material is widely applied to various fields and is also an indispensable raw material in industrial production, however, due to the self-properties, the metal is easy to generate chemical reaction or electrochemical reaction under natural environment to be corroded, so that the performance of the metal material is damaged, and the resource loss and the potential safety hazard are caused.
The metal corrosion inhibitor is one of the best corrosion prevention methods in the current industrial application, and has the advantages of low cost, high efficiency, simple and convenient practical operation, wide application range and the like compared with other corrosion prevention means such as electrochemical protection and coating corrosion prevention technologies, however, the traditional metal corrosion inhibitor has large toxicity, is easy to pollute the environment with heavy metals, has the disadvantages of high production cost, complex synthesis steps, large extraction difficulty, rust prevention, secondary pollution and the like, and has certain limitations in application and popularization.
Disclosure of Invention
The application solves the problems that the existing metal corrosion inhibitor has at least one aspect of high manufacturing and use cost, high difficulty and environmental protection.
In order to solve the problems, the application provides a preparation method of a metal corrosion inhibitor, which comprises the following steps:
step S1: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution;
step S2: and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, obtaining a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor.
Optionally, in step S2, after obtaining the second mixed solution, the method further includes: and adding a reducing agent into the second mixed solution, adding a mixed solution of ethanol and water, heating and refluxing until the reaction is complete, and separating and purifying to obtain the metal corrosion inhibitor.
Optionally, in step S1, the α -amino acid includes one of glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine or tryptophan.
Optionally, in step S2, the adding p-tert-butylbenzoyl chloride into the first mixed solution, and continuously stirring until the reaction is complete, to obtain a second mixed solution, where the second mixed solution includes:
and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, obtaining the second mixed solution, and adding excessive diluted hydrochloric acid into the second mixed solution for quenching.
Optionally, in step S2, the separation and purification includes extracting the second mixed solution, and purifying the second mixed solution by column chromatography.
Optionally, in step S1, the mixing and dissolving the α -amino acid, the alkaline reagent, and the solvent to obtain a first mixed solution, including:
mixing and dissolving the alpha-amino acid, the alkaline reagent and the solvent to obtain the first mixed solution, and placing the first mixed solution in an ice-water bath.
Optionally, in step S2, the stirring time is 6-24h.
Optionally, in step S2, the extracting the second mixed liquor includes: the second mixed liquor is extracted by ethyl acetate.
Compared with the prior art, the preparation method of the metal corrosion inhibitor has the following advantages:
the method for preparing the metal corrosion inhibitor has the advantages that the amino acid amide compound is prepared through the reaction of the alpha-amino acid, the alkaline reagent and the p-tert-butyl benzoyl chloride and is used as a metal corrosion inhibitor, N atoms and/or S atoms in the metal corrosion inhibitor can coordinate with d-space orbitals of metal ions to form coordination bonds, so that molecules of the metal corrosion inhibitor are adsorbed on the metal surface, a compact monomolecular film layer is formed on the metal surface, and corrosion mediums are isolated from the metal surface, so that the corrosion of the metal is slowed down.
The application also aims to provide a metal corrosion inhibitor which is prepared by the preparation method of the metal corrosion inhibitor.
The advantages of the metal corrosion inhibitor of the application relative to the prior art are the same as those of the preparation method of the metal corrosion inhibitor, and are not repeated here.
Another object of the application is the use of the metal corrosion inhibitor as additive for the treatment of metal surfaces.
The advantages of the application of the metal corrosion inhibitor in comparison with the prior art are the same as those of the preparation method of the metal corrosion inhibitor, and are not repeated here.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a flow chart of a method for preparing a metal corrosion inhibitor according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a method for preparing a metal corrosion inhibitor according to an embodiment of the present application;
FIG. 3 is a microscopic image of the surface morphology of untreated Q235 steel in accordance with an embodiment of the present application;
FIG. 4 shows that the Q235 steel in the first embodiment of the application is 1mol L -1 Microscopic image of the surface morphology after soaking in HCl solution for 6 hours;
FIG. 5 shows that the Q235 steel of example one of the present application contains 100mg of the metal corrosion inhibitor prepared in example one in 1mol L -1 HCl solutionSurface morphology microscopic image after soaking in the liquid for 6 hours;
FIG. 6 is a microscopic image of the surface morphology of Q235 steel according to the second embodiment of the present application.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that in the description of embodiments of the present application, the description of the term "some specific embodiments" means that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same implementations or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Referring to fig. 1, the embodiment of the application provides a preparation method of a metal corrosion inhibitor, which comprises the following steps:
step S1: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution; wherein the alkaline reagent comprises hydroxide of alkali metal elements such as sodium hydroxide, potassium hydroxide and the like, and other alkaline reagents capable of participating in the reaction.
Step S2: slowly adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, naturally recovering the reaction temperature from-10 ℃ to 5 ℃ to room temperature to obtain a second mixed solution, and separating and purifying the second mixed solution to obtain the metal corrosion inhibitor. The p-tert-butyl benzoyl chloride is slowly added into the first mixed solution containing the alpha-amino acid, so that the control of the reaction temperature is facilitated, and the reaction of the p-tert-butyl benzoyl chloride and the alpha-amino acid releases heat, so that the concentrated release of heat can be prevented by controlling the adding speed of the p-tert-butyl benzoyl chloride, and the reaction temperature is overhigh.
The method for preparing the metal corrosion inhibitor has the advantages that the amino acid amide compound is prepared through the reaction of the alpha-amino acid, the alkaline reagent and the p-tert-butyl benzoyl chloride and is used as a metal corrosion inhibitor, N atoms and/or S atoms in the metal corrosion inhibitor can coordinate with d-space orbitals of metal ions to form coordination bonds, so that molecules of the metal corrosion inhibitor are adsorbed on the metal surface, a compact monomolecular film layer is formed on the metal surface, and corrosion mediums are isolated from the metal surface, so that the corrosion of the metal is slowed down.
The metal corrosion inhibitor in the embodiment is an amino acid amide compound, is synthesized by reacting p-tert-butyl benzoyl chloride with alpha-amino acid, and generally has more than ten methods for synthesizing amide.
Because acyl chloride is easy to decompose when meeting water and becomes corresponding carboxylic acid, but because the p-tert-butyl benzoyl chloride belongs to aromatic acyl chloride, the p-tert-butyl benzoyl chloride is relatively stable and can be completely decomposed even in water for a long time, and the p-tert-butyl benzoyl chloride is selected to react in a water system in the embodiment of the application. After the reaction is finished, the rest substances are usually p-tert-butylbenzoic acid except the target product, and the substances can be recycled and used as raw materials for preparing the p-tert-butylbenzoyl chloride, so that the economy is good.
In some specific embodiments, in step S1, the alkaline reagent comprises a hydroxide of an alkali metal element. Thus, the amino acid amide compound metal corrosion inhibitor is prepared by utilizing the reducibility of the hydroxide of the alkali metal element.
In this embodiment, the alkaline reagent involved in the reaction for preparing the amide from the acyl chloride may be an inorganic base or an organic base, but the use of an inorganic base such as a hydroxide of an alkali metal element is beneficial to the subsequent operation of the reaction, simplifies the operation steps, and is beneficial to the separation and purification of the reactants.
In some specific embodiments, in step S1, the α -amino acid comprises one of glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine, or tryptophan.
Wherein the alpha-amino acids include glycine, alanine, proline, methionine, cysteine, aspartic acid, glutamic acid, phenylalanine, lysine, tryptophan and the like, and experimental steps using the above kinds of amino acids as reaction raw materials are not different, wherein corrosion inhibition efficiency is ranked from high to low: methionine (Meth) > cysteine (Cys) > proline (Pro) > alanine (Ala) > histidine (His) > lysine (2 lys) > phenylalanine (Phen) > glutamic acid (Glu) > tryptophan (Tryp), i.e. the best results were obtained when methionine was used as a reactant for the preparation of the metal corrosion inhibitor.
In some specific embodiments, in step S2, the adding p-tert-butylbenzoyl chloride to the first mixed solution and stirring until the reaction is complete, to obtain a second mixed solution, including:
and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, obtaining the second mixed solution, and adding excessive diluted hydrochloric acid into the second mixed solution for quenching.
Thus, excessive reagent in the reaction is eliminated, and the stability of the reaction product is ensured.
In some specific embodiments, in step S2, the separating and purifying includes extracting the second mixed liquor, and purifying the second mixed liquor by column chromatography. Therefore, the required product is separated through simple operation, the method is simple, and the purification rate is high.
In some specific embodiments, in step S1, the mixing and dissolving the α -amino acid, the alkaline reagent, and the solvent to obtain a first mixed solution includes:
mixing and dissolving the alpha-amino acid, the alkaline reagent and the solvent to obtain the first mixed solution, and placing the first mixed solution in an ice-water bath. In this example, since a large amount of heat is released when p-tert-butylbenzoyl chloride reacts with α -amino acid, if the temperature of the reaction system is too high, side reactions are initiated, and unnecessary products are produced, therefore, before p-tert-butylbenzoyl chloride is added, the first mixed solution is placed in an ice-water bath, the low temperature environment is favorable for inhibiting the reactivity, and the concentrated heat release is prevented from causing the temperature of the reaction system to be too high. In the prior art, a method for synthesizing the amide by adopting a low-temperature condensing agent exists, the method is usually carried out at a temperature of-20 ℃ or lower, the equipment requirement is high, the operation is complex, and the method for synthesizing the amide by adopting the p-tert-butyl benzoyl chloride is usually cooled at a temperature of 0-5 ℃, namely, the method is cooled by adopting an ice water bath in the embodiment, and the method is convenient to operate, mild in reaction and good in economy.
In some specific embodiments, in step S2, the stirring time is 6-24 hours. Thus, the p-tert-butylbenzoyl chloride is uniformly dispersed in the first mixed solution, and the reaction is more complete.
In some specific embodiments, in step S2, the extracting the second mixed liquor includes: the second mixed liquor is extracted by ethyl acetate. Thereby, the extraction rate is improved, which is beneficial to purifying the reaction product.
The preparation method of the metal corrosion inhibitor has the advantages of short synthesis steps, mild reaction conditions, simplicity and convenience in operation, wide sources, low cost, no toxicity and harm, and environment friendliness, and uses the alpha-amino acid, the alkaline reagent and the p-tert-butylbenzoyl chloride as raw materials.
The embodiment of the application also provides a metal corrosion inhibitor, which is prepared by adopting the preparation method of the metal corrosion inhibitor.
The advantages of the metal corrosion inhibitor according to the embodiment of the present application compared with the prior art are the same as those of the preparation method of the metal corrosion inhibitor, and are not described in detail herein.
The embodiment of the application provides an application of a metal corrosion inhibitor, which is used as an additive for metal surface treatment. The method is particularly suitable for fine treatment of the metal surface, including acidification of an oil gas well, corrosion prevention treatment of a circulating cooling water system, acid treatment of the metal surface, chemical cleaning of the interior of a boiler and the like.
The advantages of the application of the metal corrosion inhibitor in the embodiment of the application compared with the prior art are the same as those of the preparation method of the metal corrosion inhibitor, and are not repeated here.
The technical scheme of the application is further described below with reference to several specific embodiments, and the purposes and advantages of the application are clear.
Embodiment one:
the preparation method of the metal corrosion inhibitor comprises the following steps:
s1: 1.49g of methionine (Meth) was weighed with a balance into a 50mL round bottom flask, 0.8g of sodium hydroxide was weighed with a balance, added to the round bottom flask, and 5mL of deionized water was added for dissolution, and the round bottom flask was placed in an ice-water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using a syringe, slowly injecting the mixture into the round-bottomed flask, keeping stirring in the injection process, keeping stirring for 6 hours after the injection is finished, naturally recovering the temperature from-10 ℃ to the room temperature in the reaction process, adding excessive hydrochloric acid for quenching reaction after the reaction is finished, extracting by using ethyl acetate, and separating the metal corrosion inhibitor by using a column chromatography method after the extraction is finished.
In the embodiment, methionine (Meth) is adopted as a reaction raw material, para-tertiary butyl benzoyl chloride and methionine are adopted as raw materials in combination with the illustration of fig. 2, sodium hydroxide is added, water is adopted as a solvent, the temperature in the reaction process is naturally restored to the room temperature state from minus 10 ℃, the reaction is carried out for 6 hours, and the metal corrosion inhibitor is obtained after separation and purification.
To verify the corrosion inhibition effect of the metal corrosion inhibitors described in this example, Q235 steel was placed in 1mol L containing different concentrations of metal corrosion inhibitor -1 In HCl solution, a number of tests were performed:
1. the corrosion rate of Q235 steel was measured by the weightlessness test, and the results are shown in Table 1. As can be seen from Table 1, the Q235 steel at room temperature was at 1mol -1 The corrosion rate in HCl was 4.930gh -1 m -2 The corrosion rate in the solution added with the metal corrosion inhibitor is 2.667gh -1 m -2 、1.574gh -1 m -2 、0.384gh -1 m -2 、0.180gh -1 m -2 Compared with the blank HCl solution, the corrosion rate v of the Q235 steel in the solution added with the metal corrosion inhibitor is obviously reduced, and the greater the concentration of the metal corrosion inhibitor is, the smaller the corrosion rate of the Q235 steel is, namely the stronger the corrosion inhibition effect of the metal corrosion inhibitor is.
2. Electrochemical experiments, measuring electrokinetic polarization parameters to reflect corrosion rate, using Tafel extrapolation, the results are shown in Table 2, table 2 being the kinetic parameters of the polarization curve, showing the measured corrosion potential, corrosion current density and Tafel slope, table 2 showing that Q235 steel was at 1mol L blank at room temperature -1 The current density in HCl solution is 68.61mAcm -2 The current density in the solution added with the metal corrosion inhibitor is 28.51mAcm -2 、21.61mAcm -2 、17.23mAcm -2 、12.29mAcm -2 The corrosion current density decreases with increasing concentration of the metal corrosion inhibitor, and the concentration of the metal corrosion inhibitor is 100mgL -1 The corrosion inhibition efficiency reaches 82.12 percent.
3. Electrochemical impedance experiments, measuring impedance parameters, and the results are shown in table 3, and it can be seen from table 3 that the solution resistance decreases with the increase of the concentration of the metal corrosion inhibitor; the charge transfer resistance increases with increasing concentration of the metal corrosion inhibitor, while the constant phase angle element value decreases. The increase of the charge transfer resistance and the increase of the capacitance indicate that molecules are gradually adsorbed on the surface of the Q235 steel and gradually replace water molecules on the surface, and an adsorption film is formed on the metal surface, so that the charge transfer of the Q235 steel is blocked, the dissolution of the Q235 steel in HCl is inhibited, and the corrosion of the Q235 steel is inhibited. In addition, from experimental data, the variation trend of the corrosion inhibition efficiency is consistent with the variation trend presented by the electrokinetic polarization curve, and also consistent with the trend presented by the result in the weightlessness method test.
4. Scanning electron microscope surface morphology analysis, FIG. 3 shows the untreated Q235 steel surface morphology, FIG. 4 shows the Q235 steel at 1mol L -1 Surface morphology of Q235 steel after 6h of immersion in HCl solution, FIG. 5 shows 1mol L of the steel containing 100mg of the metal corrosion inhibitor - 1 After soaking in HCl solution for 6 hours, the surface morphology of the Q235 steel sample in the blank HCl solution is observedTo severe corrosion, a number of pronounced pit pits were visible, whereas in the HCl solution containing the metal corrosion inhibitor described above, the degree of corrosion of the Q235 steel sample surface was significantly reduced compared to the sample without the corrosion inhibitor added.
In conclusion, the amino acid amide compound prepared by taking methionine (Meth) as a reaction raw material has a certain corrosion inhibition effect as a metal corrosion inhibitor.
Embodiment two:
the difference between this embodiment and the first embodiment is that: the preparation method of the metal corrosion inhibitor of the present example uses cysteine (Cys) instead of methionine (Meth) as a reaction raw material.
The preparation method of the metal corrosion inhibitor comprises the following steps:
s1: 0.61g of cysteine (Cys) was weighed with a balance into a 50mL round bottom flask, 0.4g of sodium hydroxide was weighed with a balance, added to the round bottom flask, and 5mL of deionized water was added to dissolve the cysteine (Cys), and the round bottom flask was placed in an ice-water bath.
S2: sucking 0.98mL of p-tert-butylbenzoyl chloride by using a syringe, slowly injecting the mixture into the round-bottomed flask, keeping stirring in the injection process, keeping stirring for 24 hours after the injection is finished, naturally recovering the temperature from 5 ℃ to the room temperature in the reaction process, adding excessive hydrochloric acid for quenching reaction after the reaction is finished, extracting by using ethyl acetate, and separating by using a column chromatography after the extraction is finished to obtain the metal corrosion inhibitor.
To verify the corrosion inhibition effect of the metal corrosion inhibitor described in this example, Q235 steel was placed in 1mol lhcl solutions containing different concentrations of the metal corrosion inhibitor described above, and a number of tests were performed:
1. as a result of the weight loss test and measurement of the corrosion rate of Q235 steel, as shown in Table 1, it can be seen from Table 1 that the corrosion rate of Q235 steel in the solution to which the metal corrosion inhibitor was added was 4.902gh -1 m -2 、3.042gh -1 m -2 、1.653gh -1 m -2 、0.439gh -1 m -2 The corrosion rate v of the Q235 steel in the solution added with the metal corrosion inhibitor is obviously reduced compared with that in the blank HCl solution, and the metalThe greater the concentration of the corrosion inhibitor, the lower the corrosion rate of the Q235 steel, i.e. the stronger the corrosion inhibition of the metal corrosion inhibitor.
Table 1-weight loss test results of Q235 Steel in HCl solutions without or with Metal Corrosion inhibitors at different concentrations
2. Electrochemical experiments, measuring electrokinetic polarization parameters, the results are shown in Table 2, and the results in Table 2 indicate that the current density in the solution to which the metal corrosion inhibitor is added is 58.74mAcm -2 、39.19mAcm -2 、17.79mAcm -2 、9.64mAcm -2 The corrosion current density decreases with increasing concentration of the metal corrosion inhibitor, and the concentration of the metal corrosion inhibitor is 100mgL -1 The corrosion inhibition efficiency reaches 85.99 percent.
Table 2-kinetic potential polarization parameters of Q235 Steel in the absence or containing different concentrations of metallic Corrosion inhibitor HCl
3. Electrochemical impedance experiments, measuring impedance parameters, and the results are shown in table 3, wherein the solution resistance decreases with the increase of the concentration of the metal corrosion inhibitor; the charge transfer resistance increases along with the increase of the concentration of the metal corrosion inhibitor, and meanwhile, the element value of the constant phase angle decreases, so that experimental data show that the change trend of the corrosion inhibition efficiency is consistent with the change trend of the potentiodynamic polarization curve and the trend of the result in the weightlessness method test.
TABLE 3 impedance parameters of metallic Corrosion inhibitors without or with different concentrations in HCl solutions
4. Scanning electron microscope surface morphology analysis, FIG. 6 shows that Q235 steel contains 1mol L of 100mg of the metal corrosion inhibitor - 1 The surface morphology after soaking in HCl solution for 6 hours, from which it is observed that in the HCl solution containing the metal corrosion inhibitor, the corrosion degree of the surface of the Q235 steel sample is remarkably reduced compared with that of the sample without the corrosion inhibitor, but compared with the surface of the Q235 steel using the metal corrosion inhibitor Q235 with methionine as the raw material, the surface of the Q235 steel using the metal corrosion inhibitor with cysteine as the raw material is more regular and is closer to the surface of the original sample, which indicates that the corrosion inhibition effect of the metal corrosion inhibitor with cysteine as the raw material is poorer than that of the metal corrosion inhibitor with methionine as the raw material.
In conclusion, the amino acid amide compound prepared by taking cysteine (Cys) as a reaction raw material has a certain corrosion inhibition effect when taken as a metal corrosion inhibitor.
Embodiment III:
the difference between this embodiment and the first embodiment is that: the preparation method of the metal corrosion inhibitor of this example uses proline (Pro) instead of methionine (Meth) as a reaction raw material.
The preparation method of the metal corrosion inhibitor comprises the following steps:
s1: 1.15g of proline (Pro) was weighed with a balance into a 50mL round bottom flask, 0.8g of sodium hydroxide was weighed with a balance, added to the round bottom flask, and 5mL of deionized water was added for dissolution, and the round bottom flask was placed in an ice-water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using a syringe, slowly injecting the mixture into the round-bottomed flask, keeping stirring in the injection process, keeping stirring for 12 hours after the injection is finished, naturally recovering the temperature from-5 ℃ to the room temperature in the reaction process, adding excessive hydrochloric acid to quench the reaction after the reaction is finished, extracting by using ethyl acetate, and separating by using a column chromatography after the extraction is finished to obtain the metal corrosion inhibitor.
Embodiment four:
the difference between this embodiment and the first embodiment is that: the method for preparing the metal corrosion inhibitor of this example uses alanine (Ala) instead of methionine (Meth) as the reaction raw material.
The preparation method of the metal corrosion inhibitor comprises the following steps:
s1: 0.89g alanine (Ala) was weighed with a balance into a 50mL round bottom flask, 0.8g sodium hydroxide was weighed with a balance, added to the round bottom flask, and 5mL deionized water was added to dissolve the round bottom flask, and the round bottom flask was placed in an ice-water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using a syringe, slowly injecting the mixture into the round-bottomed flask, keeping stirring in the injection process, keeping stirring for 18 hours after the injection is finished, naturally recovering the temperature from-2 ℃ to the room temperature in the reaction process, adding excessive hydrochloric acid to quench the reaction after the reaction is finished, extracting by using ethyl acetate, and separating by using a column chromatography method after the extraction is finished to obtain the metal corrosion inhibitor.
Fifth embodiment:
the difference between this embodiment and the first embodiment is that: the preparation method of the metal corrosion inhibitor of the embodiment uses histidine (His) as a reaction raw material instead of methionine (Meth).
The preparation method of the metal corrosion inhibitor comprises the following steps:
s1: 2.04g of histidine (His) was weighed with a balance into a 50mL round bottom flask, 0.8g of sodium hydroxide was weighed with a balance, added to the round bottom flask, and 5mL of deionized water was added for dissolution, and the round bottom flask was placed in an ice-water bath.
S2: sucking 1.81mL of p-tert-butylbenzoyl chloride by using a syringe, slowly injecting the mixture into the round-bottomed flask, keeping stirring in the injection process, keeping stirring for 20 hours after the injection is finished, naturally recovering the temperature from 0 ℃ to the room temperature in the reaction process, adding excessive hydrochloric acid to quench the reaction after the reaction is finished, extracting by using ethyl acetate, and separating by using a column chromatography after the extraction is finished to obtain the metal corrosion inhibitor.
In combination with the data of the electrochemical impedance screening corresponding to the third, fourth and fifth embodiments shown in table 4, it can be observed that the amino acid amide compounds prepared by using proline (Pro), alanine (Ala) and histidine (His) as the reaction raw materials have a certain corrosion inhibition effect as the metal corrosion inhibitor.
TABLE 4 impedance parameters of non-added or added dissimilar metal Corrosion inhibitors in HCl solutions
More, other amino acids exist as reactants, and metal corrosion inhibitors with anti-corrosion effect, such as threonine, serine, tyrosine, arginine and the like, can be obtained, but more complicated and complicated steps are needed to synthesize the same type of compounds. Compared with the preparation steps of the metal corrosion inhibitor, the compound is complex to synthesize and is not simple and fast enough.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the application.

Claims (6)

1. The application of the metal corrosion inhibitor as an additive for metal surface treatment is characterized in that the preparation method of the metal corrosion inhibitor comprises the following steps:
step S1: mixing and dissolving alpha-amino acid, an alkaline reagent and a solvent to obtain a first mixed solution;
step S2: adding p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete to obtain a second mixed solution, and separating and purifying the second mixed solution to obtain a metal corrosion inhibitor;
the alkaline reagent comprises hydroxide of alkali metal element; the alpha-amino acid is at least one of methionine, cysteine, proline, alanine and histidine.
2. The use according to claim 1, wherein in step S2, p-tert-butylbenzoyl chloride is added to the first mixture and stirred until the reaction is complete, to obtain a second mixture, comprising:
and adding the p-tert-butylbenzoyl chloride into the first mixed solution, continuously stirring until the reaction is complete, obtaining the second mixed solution, and adding excessive diluted hydrochloric acid into the second mixed solution for quenching.
3. The use according to claim 1, wherein in step S2, the separation and purification comprises extracting the second mixed liquor and purifying the second mixed liquor by column chromatography.
4. The use according to claim 1, wherein in step S1, the α -amino acid, the alkaline agent and the solvent are mixed and dissolved to obtain a first mixed solution, which comprises:
mixing and dissolving the alpha-amino acid, the alkaline reagent and the solvent to obtain the first mixed solution, and placing the first mixed solution in an ice-water bath.
5. The use according to claim 1, wherein in step S2, the stirring time is between 6 and 24 hours.
6. The use according to claim 3, wherein in step S2, the extraction of the second mixed liquor is: the second mixed liquor is extracted by ethyl acetate.
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JPH10195471A (en) * 1996-12-28 1998-07-28 Neos Co Ltd Water-soluble processing oil agent
CN106986828A (en) * 2016-11-13 2017-07-28 滨州学院 A kind of utilization soybean oil prepares the method and its compounding metal inhibitor of Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor
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Publication number Priority date Publication date Assignee Title
JPH10195471A (en) * 1996-12-28 1998-07-28 Neos Co Ltd Water-soluble processing oil agent
CN106986828A (en) * 2016-11-13 2017-07-28 滨州学院 A kind of utilization soybean oil prepares the method and its compounding metal inhibitor of Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor
CN112778185A (en) * 2019-11-04 2021-05-11 游恒志 P-tert-butyl benzoic acid derivative and application thereof as metal antirust agent

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