Click-functionalized graphene oxide for inhibiting corrosion of carbon steel and method of making the same

Abstract

The present application relates to a kind of click functionalization graphene oxide for inhibiting the corrosion of carbon steel and its preparation method, and the functionalization graphene oxide at least has the following formula structure formula.The present application is provided with water injection channel in stirring shaft, hot water can be circulated in water injection channel by injecting hot water into water supply pipe until it is discharged from drain pipe, the paste of sodium ethoxylated alkyl sulfate can be heated from the inside of tank while being stirred by stirring shaft and stirring paddle, so that the paste of sodium ethoxylated alkyl sulfate is heated uniformly inside and outside, in turn prevent rancidity and other quality accidents occur, so as to improve the production quality and efficiency of sodium ethoxylated alkyl sulfate.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of corrosion inhibitor synthesis, and particularly relates to click functionalized graphene oxide for inhibiting corrosion of carbon steel and a preparation method of the click functionalized graphene oxide for inhibiting corrosion of carbon steel. BACKGROUND

[0002] Under acidic conditions or neutral conditions, metal materials are generally corroded, especially carbon steel which has excellent structural performance and is widely used in various fields. The corrosion of carbon steel not only causes huge economic losses, but also brings serious safety hazards over time, and even causes environmental pollution and ecological imbalance due to corrosion problems. Therefore, it is necessary to take effective measures to prevent corrosion of carbon steel materials.

[0003] At present, adding corrosion inhibitors is one of the most effective methods for inhibiting corrosion of carbon steel. These corrosion inhibitor molecules can form physical or chemical adsorption with the metal surface through active groups, so as to achieve the purpose of inhibiting corrosion of carbon steel.

[0004] Graphene oxide is a two-dimensional nanostructure, which has attracted a lot of attention from researchers due to its large specific surface area and excellent mechanical properties. Unlike graphene, graphene oxide contains a large number of oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy groups, which significantly enhance the dispersibility and reactivity of graphene oxide. In recent years, a large number of researchers have modified graphene oxide using its oxygen-containing functional groups, which not only can exert the functions of graphene oxide itself, but also can add new properties, greatly expanding the application range of graphene oxide. At present, the research of functionalized graphene oxide in the field of corrosion protection mainly focuses on coatings and composites, and its application as a corrosion inhibitor in the field of corrosion protection is still relatively rare.

[0005] 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. It also has great development space in the field of material protection. Therefore, it is necessary to apply click reaction to the functionalization of graphene oxide and to apply click functionalized graphene oxide as a corrosion inhibitor in the field of corrosion protection. SUMMARY

[0006] The present application provides a click functionalized graphene oxide for inhibiting corrosion of carbon steel and a preparation method of the click functionalized graphene oxide for inhibiting corrosion of carbon steel to solve the problems in the prior art.

[0007] According to one aspect of the present application, there is provided a click-functionalized graphene oxide for inhibiting corrosion of carbon steel, the functionalized graphene oxide having at least the following formula (I):

[0008]

[0009] As an improvement of the above technical solution, the graphene oxide for synthesizing the functionalized graphene oxide has the following formula (II):

[0010]

[0011] As an improvement of the above technical solution, the alkyne amine compound for synthesizing the functionalized graphene oxide has the following formula (III):

[0012]

[0013] As an improvement of the above technical solution, the azide compound for synthesizing the functionalized graphene oxide has the following formula (IV):

[0014]

[0015] According to one aspect of the present application, there is provided a preparation method of a click-functionalized graphene oxide for inhibiting corrosion of carbon steel, which is applied to the preparation of the functionalized graphene oxide, and comprises the following steps:

[0016] In step S100, 200 mg of graphene oxide is dispersed in 15 mL of DMF, and then 8.61 g of dicyclohexyl carbodiimide, 0.6 g of 4-dimethylamino pyridine and 0.3 g of propargyl amine are added to the mixed solution, the mixed solution is stirred at room temperature for 24 h, and then filtered, the product is washed with DMF, methanol and distilled water in sequence, and then vacuum dried at 40°C overnight to obtain the product of alkyne-GO;

[0017] In step S200, click chemistry reaction is performed between tosyl azide and alkyne-GO by using Cu as a catalyst, 100 mg of alkyne-GO is added to 150 mL of a round-bottom flask containing a H2O / DMF mixture, and then ultrasonic treatment is performed to make the suspension uniform.

[0018] In step S300, 1.5 g of p-toluenesulfonyl azide, 20 mg of CuSO4-5H2O and sodium ascorbate are sequentially added to the suspension, and then stirred at room temperature for 24 h, and then the mixture is centrifuged to obtain the product, and the obtained product is sequentially washed with DMF, water and ethanol;

[0019] In step S400, the product obtained in the previous step is vacuum dried at 40°C overnight.

[0020] As an improvement of the above technical solution, the synthesis route of the functionalized graphene oxide is as follows:

[0021]

[0022] As an improvement of the above technical solution, in step S200, the ultrasonic treatment time is 0.5 h.

[0023] As an improvement of the above technical solution, in step S200, the ratio of H2O and DFM in the H2O / DMF mixed solution is 2:1.

[0024] As an improvement of the above technical solution, in step S300, the centrifugal speed of the mixture is 10000 r / min.

[0025] The beneficial effects of the present application are:

[0026] 1. The functionalized graphene oxide containing triazoles is synthesized by click reaction, which can significantly inhibit the corrosion of carbon steel. The functionalized graphene oxide is first obtained by amide reaction to obtain C≡C modified graphene oxide, and then the click reaction between p-toluenesulfonyl azide and C≡C modified graphene oxide is carried out to obtain five-membered ring modified graphene oxide containing three nitrogen, i.e. click functionalized graphene oxide. The reaction process is simple to operate, can be carried out at room temperature and has almost no by-products, solves the problem of complex synthesis of traditional functionalized graphene oxide, and has significant corrosion inhibition effect on carbon steel. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The hydrophobic property of the click functionalized graphene oxide;

[0028] Figure 2 The synthesis route of the click functionalized graphene oxide. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the present application more clear and explicit, the present application will be further described in detail. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.

[0030] How to apply click reaction to the functionalization of graphene oxide, and how to apply click functionalized graphene oxide as corrosion inhibitor to the field of corrosion protection are the problems to be solved at present.

[0031] In order to solve the above problems, the present application provides a click functionalized graphene oxide for inhibiting the corrosion of carbon steel, wherein the functionalized graphene oxide has at least the following formula (I):

[0032]

[0033] First, C≡C is modified on graphene oxide through an amide reaction, then an azide compound is selected, and a click reaction between the azide compound and the alkyne-modified graphene oxide is carried out, and then the nitrogen-containing compound-modified graphene oxide obtained can effectively inhibit the corrosion of carbon steel, and the click reaction has simple reaction conditions, less required raw materials, less required raw materials, and less by-products, and the generated click functionalized graphene oxide has corrosion inhibition on carbon steel.

[0034] Specifically, first, C≡C-modified graphene oxide is obtained through an amide reaction, and then five-membered ring-modified graphene oxide containing three nitrogens, i.e., click functionalized graphene oxide, is obtained through a click reaction between p-toluenesulfonyl azide and C≡C-modified graphene oxide, and the functionalized graphene oxide has a significant inhibitory effect on the corrosion of carbon steel.

[0035] In the embodiment, the graphene oxide for synthesizing the functionalized graphene oxide has the following formula (II):

[0036]

[0037] In the embodiment, the alkyne amine compound for synthesizing the functionalized graphene oxide has the following formula (III):

[0038]

[0039] In the embodiment, the azide compound for synthesizing the functionalized graphene oxide has the following formula (IV):

[0040]

[0041] According to an aspect of the present application, a preparation method of click functionalized graphene oxide for inhibiting the corrosion of carbon steel is provided, which is applied to the preparation of the functionalized graphene oxide and comprises the following steps:

[0042] Step S100, 200 mg of graphene oxide is dispersed in 15 mL of DMF, then 8.61 g of dicyclohexyl carbodiimide and 0.6 g of 4-dimethylamino pyridine and 0.3 g of propargylamine are added to the above mixed solution, the above mixed solution is stirred at room temperature for 24 h, then filtered, the product is washed with DMF, methanol and distilled water in turn, and then vacuum dried at 40°C overnight to obtain the product of alkyne-GO;

[0043] Step S200, using Cu catalysis, so that toluenesulfonyl azide and alkyne-GO between the click chemistry reaction, in 150 mL round bottom flask, 100 mg of alkyne-GO with H2O / DMF mixture, ultrasonic treatment 0.5 h, make it suspended evenly.

[0044] Step S300, 1.5 g of p-toluenesulfonyl azide, 20 mg of CuSO4-5H2O and sodium ascorbate salt are added to the above suspension in turn, then stirred at room temperature for 24 h, then the mixture is centrifuged at a speed of 10000 r / min to obtain the product, and the obtained product is washed with DMF, water and ethanol in turn;

[0045] Step S400, the product obtained in the above step is placed in a vacuum dryer at 40℃ for one night.

[0046] In combination with the accompanying Figure 2 In this embodiment, the synthesis route of the functionalized graphene oxide is as follows:

[0047]

[0048] As an improvement of the above technical solution, in step S200, the ratio of H2O and DFM in the H2O / DMF mixture is 2:1.

[0049] In combination with the accompanying Figure 1 Further explanation of the hydrophobicity of the click functionalized graphene oxide is made in combination with Fig. a and Fig. b in the accompanying drawings.

[0050] The carbon steel is immersed in 1M HCL containing and not containing 30 ppm click functionalized graphene oxide respectively, and after 3 h, the N80 carbon steel in the two different cases is taken out for hydrophobicity comparison test.

[0051] Figure 1 Fig. (a) and (b) in the accompanying drawings respectively show the contact angle of the carbon steel surface under the conditions of blank and 30 ppm inhibitor.

[0052] As can be seen from the pictures, the water droplets in Fig. (b) have a smaller contact angle with the N80 carbon steel surface, that is, after being immersed in 1M HCL containing 30 ppm click functionalized graphene oxide for 3 h, the contact angle of the water droplets with the carbon steel surface is obviously larger than that of the carbon steel in the blank solution, which shows that the click functionalized graphene oxide can be adsorbed on the carbon steel surface, and has a certain hydrophobicity, which can improve the hydrophobicity of the carbon steel surface, further hinder the corrosion of the corrosion medium to the carbon steel, and thus play an excellent corrosion inhibition effect.

[0053] In combination with Table 1 below, the corrosion inhibition performance of the click functionalized graphene oxide under acidic conditions is further explained.

[0054] The effect of click-functionalized graphene oxide of the present invention on the corrosion of carbon steel was evaluated by the weight loss method in 1M HCl solution at 25℃, with a weight loss time of 3h.

[0055] Table 1 shows the comparative evaluation results of carbon steel immersed in a 1MHCL solution containing 30 ppm click-functionalized graphene oxide and carbon steel in the blank condition in this invention. By comparing the weight loss data of the coated plates in the 1MHCL system, it can be seen that when 30 ppm click-functionalized graphene oxide is contained, the corrosion rate of carbon steel is significantly reduced, which is consistent with the conclusion that click-functionalized graphene oxide can improve the hydrophobicity of carbon steel.

[0056] Table 1:

[0057]

[0058] Combined with appendix Figure 3 Figures a and b further illustrate the corrosion inhibition performance of click-functionalized graphene oxide under acidic conditions.

[0059] The effect of click-functionalized graphene oxide on the corrosion of carbon steel was investigated by electrochemical measurement in 1MHCl solution at 25℃. The circuit was kept stable for 1 hour before impedance measurement.

[0060] exist Figure 3 The paper presents the comparative evaluation results of carbon steel immersed in a 1MHCl solution containing 30ppm click-functionalized graphene oxide, a 1MHCl solution containing 30ppm graphene oxide, and carbon steel under blank conditions.

[0061] As can be seen, compared with the blank and the case with added graphene oxide, the diameter of the impedance arc increased significantly after adding 30 ppm of click-functionalized graphene oxide, which further illustrates the excellent protective effect of click-functionalized graphene oxide.

[0062] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Click-functionalized graphene oxide for inhibiting corrosion of carbon steel, characterized in that, The functionalized graphene oxide has at least the following formula (I):

2. The click-functionalized graphene oxide for inhibiting corrosion of carbon steel according to claim 1, wherein, The graphene oxide used to synthesize the functionalized graphene oxide has the following formula (II):

3. The click-functionalized graphene oxide for inhibiting corrosion of carbon steel according to claim 1, wherein the click-functionalized graphene oxide is characterized by, The alkyne amine compound used to synthesize the functionalized graphene oxide has the following formula (III):

4. The click-functionalized graphene oxide for inhibiting corrosion of carbon steel according to claim 1, wherein the carbon steel is a low carbon steel. The azide compound used to synthesize the functionalized graphene oxide has the following formula (IV):

5. A method for preparing click-functionalized graphene oxide for inhibiting corrosion of carbon steel, characterized in that, The preparation of the functionalized graphene oxide according to any one of claims 1-4 comprises the following steps: In step S100, 200 mg of graphene oxide is dispersed in 15 mL of DMF, then 8.61 g of dicyclohexyl carbodiimide and 0.6 g of 4-dimethylamino pyridine and 0.3 g of propargyl amine are added to the mixed solution, the mixed solution is stirred at room temperature for 24 h, then filtered, the product is washed with DMF, methanol and distilled water in sequence, then vacuum dried at 40°C overnight to obtain the product of alkyne-GO; In step S200, click chemistry reaction is carried out between tosyl azide and alkyne-GO by using Cu as catalyst, 100 mg of alkyne-GO is added to 150 mL of round bottom flask with H2O / DMF mixed solution, after ultrasonic treatment, it is suspended uniformly; In step S300, 1.5 g of p-toluenesulfonyl azide, 20 mg of CuSO4-5H2O and sodium ascorbate are added to the above suspension in sequence, then stirred at room temperature for 24 h, then the mixture is centrifuged to obtain the product, the obtained product is washed with DMF, water and ethanol in sequence; In step S400, the product obtained in the previous step is vacuum dried at 40°C overnight.

6. The preparation method according to claim 5, characterized in that, The synthesis route of the functionalized graphene oxide is as follows:

7. The preparation method according to claim 5, characterized in that, In step S200, the ultrasonic treatment time is 0.5 h.

8. The preparation method according to claim 5, characterized in that, In step S200, the ratio of H2O and DFM in the H2O / DMF mixed solution is 2:

1.

9. The preparation method according to claim 5, characterized in that, In step S300, the centrifugal speed of the mixture is 10000 r / min.

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