A sulfide compound for inhibiting copper corrosion, a preparation method thereof, and application thereof

Abstract

The application provides a sulfide compound for inhibiting copper corrosion, and a structural formula of the sulfide compound is as follows: The application adds mercaptan compounds, alkyne and a photoinitiator into ethanol to obtain a mixed solution, then immerses a copper metal sheet into the mixed solution, and under the action of ultraviolet light, a click reaction occurs to synthesize the sulfide compound containing a C-S-C bond, so as to inhibit the corrosion of the copper metal and protect the copper metal, and the sulfide compound has a good effect of inhibiting the corrosion of the copper.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new materials, in particular to a sulfide compound for inhibiting copper corrosion, a preparation method and application thereof. BACKGROUND

[0002] Metal copper has excellent electrical conductivity, thermal conductivity, ductility, weldability and the like, and thus is widely used in marine environments. There are a large number of Cl- in marine environments, which can destroy the metal surface film and easily cause corrosion of the metal. Adding corrosion inhibitors is the most convenient, efficient and economical means to inhibit material corrosion, and has been widely used in industry. However, the adsorption film formed by most organic corrosion inhibitors on the metal surface is uneven, resulting in poor effect of inhibiting copper corrosion.

[0003] Therefore, how to enhance the inhibiting effect on copper corrosion has become a problem to be solved.

[0004] The above information disclosed in the background is only used to strengthen the understanding of the background of the present application, and thus it can contain information which is not prior art known to those of ordinary skill in the art. SUMMARY

[0005] The present application provides a sulfide compound for inhibiting copper corrosion, a preparation method and application thereof to solve the problems existing in the prior art.

[0006] In a first aspect, the present application provides a sulfide compound for inhibiting copper corrosion, and the structural formula of the sulfide compound is:

[0007]

[0008] In a second aspect, the present application provides a preparation method of a sulfide compound for inhibiting copper corrosion, comprising the following steps:

[0009] S1, adding a thiol compound, an alkyne and a photoinitiator into ethanol to obtain a mixed solution;

[0010] The weight ratio of the thiol compound to the alkyne is 2.5-2.7:1, and the weight ratio of the photoinitiator to the thiol compound is 1:10;

[0011] S2, immersing a copper metal sheet into the mixed solution, and generating a click reaction under the action of ultraviolet light, so that the sulfide compound is generated on the surface of the copper metal sheet, and the structural formula of the sulfide compound is:

[0012]

[0013] In some embodiments, the structural formula of the thiol compound is:

[0014]

[0015] In some embodiments, the structure of the alkyne is:

[0016]

[0017] In some embodiments, the power of the ultraviolet light is 10 W.

[0018] In some embodiments, the reaction time of the click reaction is 1.5 h.

[0019] In some embodiments, the thiol compound is any one of furfuryl mercaptan, dithiothreitol, beta-mercaptopropionic acid and 2-mercaptoethanol.

[0020] In some embodiments, the alkyne is any one of 3,3-dimethyl-1-butyne, 1,4-butyne diol, 2-pentynoic acid, propargyl acid and 3-butyne-1-ol.

[0021] In some embodiments, the photoinitiator comprises any one of OMBB, BDK, EDB and TPO.

[0022] In a third aspect, the application further provides a use of the sulfide compound obtained by the preparation method in inhibiting copper corrosion.

[0023] The sulfide compound provided by the application for inhibiting copper corrosion has the structure of:

[0024]

[0025] The application adds a thiol compound, an alkyne and a photoinitiator into ethanol to obtain a mixed solution, then immerses a copper metal sheet into the mixed solution, and under the action of ultraviolet light, a click reaction occurs to synthesize a sulfide compound containing a C-S-C bond, which is used for inhibiting the corrosion of copper metal and plays a protective role on copper metal, and has a good effect of inhibiting copper corrosion. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and serve to explain the principles of the application.

[0027] Figure 1 A step flow chart of a preparation method of a sulfide compound for inhibiting copper corrosion provided by the application is shown in the figure.

[0028] Figure 2The contact angles of (a), (b) and (c) in the figure are the contact angles of the blank copper metal, the copper metal under light and the copper metal under dark, respectively.

[0029] The specific embodiments of the present application have been shown by the above figures, and will be described in more detail hereinafter. The figures and the written description are not intended to limit the scope of the present application in any way, but to illustrate the concept of the present application for the person skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION

[0030] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the accompanying drawings of the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the protection scope of the present application.

[0031] The terms used in the embodiments of the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the present application. The singular forms "a" and "the" used in the embodiments of the present application are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0032] It should also be noted that the terms "comprising", "including", or any other variant thereof are intended to cover non-exclusive inclusion, so that the product or system including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or further includes the elements inherent to such product or system. Without more limitations, the element defined by the sentence "including a" does not exclude the presence of another identical element in the product or system including the element.

[0033] Detailed analysis of the background problem:

[0034] Self-assembled films have attracted a lot of attention due to their simple synthesis, low cost, high efficiency and other characteristics. Self-assembled film technology refers to the process that the active end group of molecules spontaneously forms a stable and ordered molecular film on the surface of a metal substrate. This layer of film can prevent corrosive media from approaching the metal surface, thereby achieving the purpose of corrosion inhibition. As a new technology for corrosion protection, self-assembly technology has quickly become the research focus of related disciplines.

[0035] The click reaction is a simple and effective new synthesis method, which has the advantages of mild reaction conditions, high yield, and almost no by-product generation, and has attracted a lot of attention from researchers in recent years, and has shown great development space in the field of material protection. The present application starts from this, and by introducing ultraviolet light into the system, the thiol-alkyne click reaction can be directly induced to occur on the metal surface, thereby forming a layer of thioether self-assembled film on the copper surface.

[0036] The technical solutions of the present application and how the technical solutions of the present application solve the above technical problems will be described in detail below with specific examples. The following specific examples can be combined with each other, and the same or similar concepts or processes can not be described again in some examples. The embodiments of the present application will be described below with reference to the accompanying drawings.

[0037] The present application provides a thioether compound for inhibiting copper corrosion, and the structural formula of the thioether compound is:

[0038]

[0039] Figure 1 The step flow chart of the preparation method of the thioether compound for inhibiting copper corrosion provided by the present application is shown in Figure 1 The present application also provides a preparation method of a thioether compound for inhibiting copper corrosion, comprising the following steps:

[0040] S1, adding a thiol compound, an alkyne and a photoinitiator into ethanol to obtain a mixed solution;

[0041] The weight ratio of the thiol compound to the alkyne is 2.5-2.7:1, and the weight ratio of the photoinitiator to the thiol compound is 1:10;

[0042] S2, immersing a copper metal sheet in the mixed solution, and the thioether compound is generated on the surface of the copper metal sheet under the action of ultraviolet light, and the structural formula of the thioether compound is:

[0043]

[0044] The present application adds a thiol compound, an alkyne and a photoinitiator into ethanol to obtain a mixed solution, and then immerses a copper metal sheet in the mixed solution, and the thioether compound containing C-S-C bond is synthesized by click reaction under the action of ultraviolet light, which is used for inhibiting the corrosion of copper metal and plays a protective role for copper metal, and has a good effect of inhibiting copper corrosion.

[0045] It should be noted that in the preparation method of the sulfide compound in the present application, the sulfide compound is adsorbed on the surface of copper to form a self-assembled film, which can better inhibit the corrosion of copper.

[0046] In some embodiments, the structure of the thiol compound is:

[0047]

[0048] In some embodiments, the structure of the alkyne is:

[0049]

[0050] In some embodiments, the power of the ultraviolet light is 10W.

[0051] In some embodiments, the reaction time of the click reaction is 1.5h.

[0052] Specifically, in the embodiments of the present application, the ethanol is only used as a solvent, and there is no specific requirement for the proportion of the ethanol.

[0053] In some embodiments, the thiol compound is any one of furfuryl mercaptan, dithiothreitol, beta-mercaptopropionic acid and 2-mercaptoethanol.

[0054] In some embodiments, the alkyne is any one of 3,3-dimethyl-1-butyne, 1,4-butyne diol, 2-pentynoic acid, propargyl acid and 3-butyne-1-alcohol.

[0055] Specifically, in the embodiments of the present application, when the thiol compound is furfuryl mercaptan and the alkyne is 3,3-dimethyl-1-butyne, the prepared sulfide compound has better corrosion resistance.

[0056] It should be noted that the sulfide compound prepared by the present application can effectively inhibit the corrosion of copper, and the click reaction in the preparation process has a short reaction time, requires less raw materials, has a simple preparation process, generates less by-products, and the corrosion inhibition effect of the self-assembled film of the obtained sulfide compound on copper is very significant.

[0057] In some embodiments, the photoinitiator includes any one of OMBB, BDK, EDB and TPO.

[0058] Specifically, in the embodiments of the present application, the temperature in the preparation process is room temperature.

[0059] More specifically, the room temperature in the present application is 20-25℃.

[0060] It should be further noted that the room temperature can be 20℃, 22℃, 25℃, etc.

[0061] The application also provides application of the sulfide compound obtained according to the method to copper corrosion inhibition.

[0062] The application uses furfuryl mercaptan and 3,3-dimethyl-1-butynyl as monomers, and initiates click reaction of the two monomers on the surface of copper metal under ultraviolet light through a photoinitiator, so as to form a dense self-assembled film on the surface of copper, which is a sulfide compound and has a good inhibition effect on copper corrosion.

[0063] The following are specific examples:

[0064] Example 1: Preparation of a sulfide self-assembled film

[0065] 1) 70 ppm furfuryl mercaptan, 35 ppm 3,3-dimethyl-1-butynyl, and 7 ppm BDK (photoinitiator) were added to a three-necked quartz bottle containing 50 ml of ethanol, a T2 red copper electrode (exposed area of 1 cm x 1 cm) was polished with 400#, 800#, and 1200# metallographic sandpaper in turn, and then the surface of the electrode was wiped with ethanol to remove grease on the surface of the electrode, and the treated electrode was immersed in the mixed solution.

[0066] 2) A 10W ultraviolet lamp was used to irradiate the three-necked quartz bottle containing the mixed solution, and under the ultraviolet light, the mercaptan and alkyne monomers adsorbed on the surface of the copper would undergo click reaction, thereby forming a sulfide self-assembled film. In the application, the self-assembled film formed on the metal surface after 1.5h of light irradiation has the best effect on metal corrosion.

[0067] Example 2: Hydrophobicity exploration of the sulfide self-assembled film

[0068] The metal copper with a dense sulfide self-assembled film grown on the surface obtained according to Example 1 was subjected to hydrophobicity comparison test with a blank electrode and a T2 red copper surface immersed in the mixed solution in the dark for 1.5h. Figure 2 The contact angles of (a), (b), and (c) in FIG. 1 are the contact angles of the surface of the blank copper metal, the copper metal under light irradiation, and the copper metal under dark condition, respectively. As shown in FIG. 1, the contact angle of the copper metal under ultraviolet light irradiation is significantly increased, indicating that the sulfide self-assembled film grown on the surface can improve the hydrophobicity of the copper metal surface, hinder the corrosion of the corrosion medium to the copper, and thus play an excellent corrosion inhibition effect. Figure 2

[0069] Example 3: Inhibition performance evaluation of the sulfide self-assembled film under neutral conditions

[0070] ​The self-assembled film of the present application was evaluated for its effect on the corrosion of copper by weight loss coupon method in 3.5% NaCl solution at 25°C, and the weight loss coupon time was 24 hours. Table 1 shows the comparative evaluation results of the copper metal with the self-assembled film on the surface and the blank sample in the present application. It can be seen from the comparison of the weight loss coupon data in 3.5% NaCl system that the corrosion rate of copper can be significantly reduced after the growth of the sulfide self-assembled film on the metal surface, which is consistent with the result of the hydrophobicity of the metal surface. Figure 2

[0071] Table 1

[0072]

[0073] It should be understood that, although each step in the flowchart in the above embodiments is shown in sequence according to the direction of the arrow, these steps are not necessarily executed in sequence according to the direction of the arrow. Unless explicitly stated herein, the execution of these steps is not strictly limited in sequence, and they can be executed in other sequences. Moreover, at least part of the steps in the figure can include multiple sub-steps or multiple stages, which are not necessarily executed at the same time, but can be executed at different times, and the execution sequence is not necessarily sequential, but can be executed in rotation or alternation with at least part of other steps or sub-steps or stages of other steps.

[0074] Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the application being indicated by the following claims.

[0075] It should be understood that the application is not limited to the precise construction that has been described above and shown in the accompanying drawings, and that various modifications and changes can be made by those skilled in the art without departing from the scope of the application. The scope of the application is limited only by the appended claims.​

Claims

1. A sulfide compound for inhibiting copper corrosion, characterized in that, The structural formula of the thioether compound is: 。 2. A method for producing a sulfide compound for inhibiting corrosion of copper, characterized by, The method comprises the following steps: S1, adding a thiol compound, an alkyne and a photoinitiator into ethanol to obtain a mixed solution; The weight ratio of the thiol compound to the alkyne is 2.5-2.7:1, and the weight ratio of the photoinitiator to the thiol compound is 1:10; The structural formula of the thiol compound is: ； The structural formula of the alkyne is: ； The photoinitiator is BDK; S2, immersing a copper metal sheet into the mixed solution to generate a click reaction under the action of ultraviolet light, the power of the ultraviolet light is 10 W, and the surface of the copper metal sheet generates the thioether compound, the structural formula of the thioether compound is: 。 3. The preparation method according to claim 2, characterized in that, The reaction time of the click reaction is 1.5 h.

4. Application of the thioether compound in claim 1 to copper corrosion inhibition.

Images