A method for preparing a triazole corrosion-inhibiting polymer film by electrochemically mediating atom transfer radical polymerization in situ on a copper surface

Abstract

The application relates to a method for preparing a triazole corrosion-inhibiting polymer film in situ on a copper surface through electrochemically mediated atom transfer radical polymerization, which comprises the following steps: adding a solution containing propargyl acrylate, p-toluenesulfonyl azide, a catalyst, a ligand and potassium bromide into a reactor; placing a copper sheet with an initiator assembled on the surface into the reactor to perform a reaction under the mediation of electrochemistry; taking out the copper sheet, washing and drying the copper sheet, so that the copper sheet surface is covered with a triazole corrosion-inhibiting polymer film. Compared with the prior art, the electrochemically mediated atom transfer radical polymerization technology is adopted to prepare a triazole corrosion-inhibiting polymer film in situ on the copper surface, and compared with the prior art disclosed in the prior art, the method does not need to remove oxygen, can be performed at normal temperature and pressure, and is simple to operate. Meanwhile, the click chemistry reaction and the polymerization reaction have the same Cu(I) catalytic system, the click chemistry reaction and the polymerization reaction can be simultaneously performed through a one-pot method, the amount of the catalyst used is smaller, and the method is more environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of metal corrosion protection technology, specifically to a method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization. Background Technology

[0002] Triazole compounds are highly effective corrosion inhibitors for copper and its alloys. Taking benzotriazole (BTAH) as an example, it is generally believed that BTAH mainly forms stable chemical bonds between the lone pair electrons of the nitrogen atom in the triazole ring and the empty orbitals of the copper atom, forming an insoluble [Cu(I)BTA] compound on the copper surface. n A chain-like polymeric film is formed, thereby inhibiting copper corrosion. [Cu(I)BTA] n The degree of polymerization is crucial for the corrosion inhibition performance of triazole films. Previously, the degree of polymerization was mainly controlled by self-assembly methods to prepare triazole corrosion inhibitor films. However, since self-assembly is a spontaneous process to some extent, the orderliness, orientation, and functionality of the assembled films are easily disrupted, thus affecting the regularity and stability of the corrosion inhibitor films. Therefore, more effective external field control methods are needed.

[0003] Patent application number 202211522530.3 discloses a method for preparing a triazole-based corrosion-inhibiting polymeric film on a copper surface. The method involves dissolving propyne acrylate and p-toluenesulfonyl azide in a solvent and reacting them under the action of a catalyst to obtain a polymerizable monomer containing a triazole ring. The monomer and 2,2'-bipyridine are then dissolved in a solvent, and an initiator, catalyst, and reducing agent are added. An atom transfer radical polymerization reaction is carried out under anaerobic conditions to obtain a triazole-based corrosion-inhibiting polymer solution. A triazole-based corrosion-inhibiting polymeric film is then prepared on the copper surface using a self-assembly technique. Patent application number 202310764027.7 discloses a method for in-situ initiation preparation of a triazole corrosion-inhibiting polymeric film on a copper surface. A pre-treated copper sheet is immersed in an initiator solution to obtain a copper sheet with an initiator assembled on its surface. Then, the copper sheet, a polymerizable monomer containing a triazole ring, a ligand, and a catalyst are added to a solvent, and a polymerization reaction is carried out under the action of a catalyst. After washing and drying, a triazole corrosion-inhibiting polymeric film is obtained. Both methods can effectively control the degree of polymerization and properties of the prepared triazole corrosion-inhibiting polymer film. However, both methods use the traditional atom transfer radical polymerization (ATRP) technology and require the prior synthesis of triazole polymerizable monomers through click chemistry. They have disadvantages such as large Cu(I) catalyst usage, poor controllability in the polymer film preparation process, the need for inert atmosphere protection during polymerization, and low monomer utilization. Summary of the Invention

[0004] The purpose of this invention is to overcome at least one of the defects of the prior art by providing a method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization.

[0005] In recent years, to address the shortcomings of traditional ATRP methods, new methods utilizing external stimuli to regulate the ATRP activation / deactivation process have been reported and have attracted widespread attention. These include ARGET (activators regenerated by electron transfer) ATRP, ICAR (initiators for continuous activator regeneration) ATRP, SARA (supplemental activator and reducing agent) ATRP, electrochemically mediated ATRP (E-ATRP), and photochemically mediated ATRP. These techniques share the common feature of using external stimuli to regulate the polymerization process in situ, while overcoming many shortcomings of traditional ATRP methods, such as reducing catalyst usage, simplifying the polymerization process, and eliminating the need for deoxygenation. Among these, E-ATRP offers significant advantages; the polymerization process can be controlled through electrochemical parameters, enabling simple "automated" operation by setting these parameters. By applying a suitable voltage (such as the reduction potential of the catalyst) to a solution containing initiators, monomers, and catalysts, the active and dormant species can be electrochemically reversed, allowing the preparation of various types of polymer films. The inventors discovered in experiments that using E-ATRP to in-situ initiate the preparation of triazole corrosion-inhibiting polymer films on copper surfaces can overcome the shortcomings of traditional polymerization methods. It can easily achieve the switching between "ON" and "OFF" of the polymerization reaction and realize the control of polymerization kinetics, which has greater significance for practical production applications.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] One objective of this invention is to provide a method for preparing a triazole corrosion-inhibiting polymer film on a copper surface through electrochemically mediated atom transfer radical polymerization, comprising the following steps:

[0008] Step 1: Add the solution containing propyne acrylate, p-toluenesulfonyl azide, catalyst, ligand and potassium bromide to the reactor;

[0009] Step 2: Immerse the pretreated copper sheet in the initiator solution to allow the initiator to assemble on the surface of the copper sheet. After washing, you will get a copper sheet with the initiator assembled on its surface.

[0010] Step 3: Place the copper sheet with the initiator assembled on its surface into the reactor and allow it to react fully under the mediation of electrochemistry. After the copper sheet is removed, washed, and dried, a layer of triazole corrosion inhibitor polymer film is coated on the surface of the copper sheet.

[0011] More specifically, a method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization includes the following steps:

[0012] Step 1: Using a one-pot method, dissolve p-toluenesulfonyl azide, propyne acrylate, copper bromide, ligand (tris(2-(dimethylazoyl)ethyl)amine), and potassium bromide in a solvent to obtain the solution required for the reaction.

[0013] Step 2: Immerse the pretreated copper sheet in the initiator solution to allow the initiator to assemble on the surface of the copper sheet. After washing, you will get a copper sheet with the initiator assembled on its surface.

[0014] Step 3: Pour the solution required for the reaction into the reactor, add the copper sheet with the initiator assembled on its surface into the reactor containing the solution required for the reaction, and under the mediation of electrochemistry and the catalysis of Cu(I), the click chemical reaction and the polymerization reaction proceed simultaneously. After controlling different reaction times, washing and drying, triazole corrosion-inhibiting polymer films of different thicknesses are obtained. The corrosion-inhibiting film prepared on the copper surface is named P-TTMA, and the corresponding copper sample is named P-TTMA-Cu.

[0015] The one-pot method used can simultaneously carry out click chemistry and polymerization reactions at room temperature and normal pressure, and the operation process is simple.

[0016] Further, the molar concentration ratio of propyne acrylate, p-toluenesulfonyl azide, and catalyst is (900-1000):(450-500):1. In a preferred embodiment of the present invention, the molar concentrations of propyne acrylate, p-toluenesulfonyl azide, and catalyst are 9.06M, 4.92M, and 9.96 × 10⁻⁶ M, respectively. -3 M.

[0017] Furthermore, the catalyst is copper bromide.

[0018] Furthermore, in order to convert divalent copper into monovalent copper by gaining electrons, potassium bromide is added in step one. The potassium bromide is a supporting electrolyte, which improves the conductivity of the solution and does not participate in the electrochemical reaction itself. In addition, since the catalyst is copper bromide, potassium bromide is chosen as the supporting electrolyte to eliminate the interference of impurities on the experiment.

[0019] Furthermore, the ligand is tris(2-(dimethylazo)ethyl)amine, which forms a complex with copper ions and cuprous ions to ensure the stability of the two ions; in addition, the ligand also helps the catalyst to dissolve and forms a catalytic center with the catalyst.

[0020] Furthermore, the solution used to dissolve propyne acrylate, p-toluenesulfonyl azide, the catalyst, the ligand, and potassium bromide is an aqueous ethanol solution; the volume ratio of ethanol to water in the aqueous ethanol solution is (0.5–2):1.

[0021] Further, the copper sheet pretreatment steps are as follows: the copper sheet is polished sequentially using 800, 1200, 1500, and 2000 grit sandpaper, and then rinsed clean with deionized water, anhydrous ethanol, and deionized water. Preferably, the copper sheet is a circular copper sheet with a diameter of 15 mm and a thickness of 2 mm.

[0022] Furthermore, the initiator solution is an aqueous solution of ethanol containing 2-bromoisobutyric acid 2-hydroxyethyl ester.

[0023] Furthermore, the volume ratio of anhydrous ethanol to water in the ethanol-water solution is (3-5):1.

[0024] Furthermore, in step three, the reaction time is 1 to 7 hours.

[0025] The second objective of this invention is to provide a triazole corrosion-inhibiting polymer film, which is prepared by the method described above. When coated on metallic copper, it can be used for corrosion protection of copper products.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] (1) This invention employs electrochemically mediated atom transfer radical polymerization technology to in-situ initiate the preparation of triazole corrosion-inhibiting polymer films on copper surfaces. Compared with existing technologies, this method eliminates the need for oxygen removal and allows the reaction to proceed in a reactor at ambient temperature and pressure, simplifying the operation. Furthermore, the click chemistry and polymerization reactions utilize the same Cu(I) catalytic system, enabling simultaneous click chemistry and polymerization reactions in a "one-pot" process, requiring less catalyst and making it more environmentally friendly.

[0028] (2) By controlling the polymerization reaction time, this invention can obtain polymer films with different thicknesses and different corrosion inhibition properties, providing a new approach for the preparation of triazole corrosion inhibition films on copper surfaces.

[0029] (3) Without affecting the performance of copper, the present invention uses electrochemically mediated atom transfer radical polymerization technology to prepare a triazole corrosion inhibitory polymer film on the surface of copper sheet, which exhibits excellent corrosion inhibition performance for copper in simulated seawater. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the reactor used in Example 1, where the reaction can be carried out in air;

[0031] Figure 2 In Example 1, cyclic voltammetry curves were recorded on a platinum working electrode before the polymerization reaction, showing the potential for Cu(II) to be reduced to Cu(I);

[0032] Figure 3 This is a schematic diagram of the in-situ preparation of a triazole corrosion-inhibiting polymer film on a copper surface using electrochemically mediated atom transfer radical polymerization technology as described in Example 1.

[0033] Figure 4 This is a graph showing the change in the thickness of the P-TTMA film on the copper surface as a function of reaction time in Example 1.

[0034] Figure 5 Electrochemical impedance spectroscopy (EIS) of blank copper and P-TTMA-Cu-1, P-TTMA-Cu-2, P-TTMA-Cu-3, P-TTMA-Cu-4, P-TTMA-Cu-5, P-TTMA-Cu-6, and P-TTMA-Cu-7 copper electrodes from Example 1 after immersion in 3.5 wt% NaCl solution for 1 hour.

[0035] Figure 6 This is a partially magnified electrochemical impedance spectroscopy (EIS) image of the blank copper and P-TTMA-Cu-1, P-TTMA-Cu-2, P-TTMA-Cu-3, P-TTMA-Cu-4, P-TTMA-Cu-5, P-TTMA-Cu-6, and P-TTMA-Cu-7 copper electrodes from Example 1, after immersing them in a 3.5 wt% NaCl solution for 1 hour.

[0036] The numbers in the diagram are as follows: 1-fine adjustment knob, 2-pressure gauge, 3-working electrode, 4-adjustment hole, 5-top cover plate, 6-tank body, 7-bottom frustum, 8-bottom cylindrical container, 9-rotor, 10-shelf, 11-adjustment hole, 12-pair electrode. Detailed Implementation

[0037] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0038] Example 1

[0039] Step 1, such as Figure 2As shown, cyclic voltammetry curves were recorded on a platinum working electrode before the polymerization reaction, revealing the potential for the reduction of Cu(II) to Cu(I). It can be seen that in this system, the potential for the reduction of Cu(II) to Cu(I) occurs at 0.23 V, and the subsequent reaction proceeds at this potential.

[0040] Step 2: Prepare the reaction solution by ultrasonically stirring 2 mL of p-toluenesulfonyl azide, 1.1 mL of propyne acrylate, 0.0446 g of copper bromide, 5 μ L of ligand (tris(2-(dimethylazoyl)ethyl)amine), 12 g of potassium bromide, and 100 mL each of ethanol and deionized water.

[0041] Step 3: Use a copper sheet with a diameter of 15mm and a thickness of 2mm as the working electrode. Polish the copper sheet in sequence with 600 grit, 1000 grit, 1500 grit and 2000 grit, then clean it in sequence with deionized water, ethanol and deionized water, and blow it dry with nitrogen for later use.

[0042] Step 4: Immerse the pretreated copper sheet from Step 3 in a H2O / ethanol solution (1:4, V / V) of 2-bromoisobutyric acid 2-hydroxyethyl ester initiator and react for 12 hours. Then wash with deionized water, ethanol, and deionized water in sequence, and dry with nitrogen to obtain a copper sheet with initiator assembled on its surface.

[0043] Step 5: Under room temperature and normal pressure conditions, pour the solution required for the reaction into the reactor, and place the copper sheet with the initiator assembled on its surface in Step 4 into the reactor. The solution should cover the copper sheet. Use a two-electrode system to perform electrochemical current-time curve testing.

[0044] See Figure 1 In the experiment, the entire reactor was placed on a magnetic stirrer. The reaction solution was continuously stirred by the rotor 9 and the magnetic stirrer, and the reaction was fully completed. A movable bottom cylindrical container 8 was installed at the center of the bottom frustum 7. Inside the bottom cylindrical container 8 was a grid-shaped shelf 10 that could hold four copper plates. Platinum electrodes were placed on the shelf 10 as working electrodes 3 and below as counter electrodes 12. Working electrodes 3 and counter electrodes 12 were connected to the Chenhua electrochemical workstation in the external environment through adjustment holes 4 and 11, respectively. Working electrode 3 was connected to a green clip, and counter electrode 12 was connected to red and white clips.

[0045] Simulated reaction times of 1h, 2h, 3h, 4h, 5h, 6h, and 7h were performed respectively. After the experiment, the copper sheet was removed and washed sequentially with deionized water, ethanol, and then deionized water. It was then placed in a vacuum drying oven and dried under vacuum at 60℃ for 12h. The copper samples obtained were named P-TTMA-Cu-1, P-TTMA-Cu-2, P-TTMA-Cu-3, P-TTMA-Cu-4, P-TTMA-Cu-5, P-TTMA-Cu-6, and P-TTMA-Cu-7 in ascending order of reaction time.

[0046] Under E-ATRP conditions, the film thickness varies with time and between adjacent integer time intervals. In first-order kinetics, polymer growth is essentially linear with time, and this linear growth continues for up to 6 hours. At 7 hours, the film thickness growth significantly decreases. The results are shown in [Figure number missing]. Figure 4 .

[0047] The corrosion inhibition performance of P-TTMA on a copper substrate was tested using a 3.5 wt.% NaCl solution as the corrosive medium. The AC impedance of P-TTMA-Cu electrodes prepared at different reaction times after immersion in the corrosive medium for 1 hour was measured electrochemically. The results are shown in [Figure number missing]. Figure 5 , Figure 5 B is Figure 5 A magnified view of the Cu and P-TTMA-Cu-1 curves in section A. Obvious capacitive arcs can be observed on the impedance spectra corresponding to each electrode. The capacitive arc is largest for P-TTMA-Cu-7, followed by P-TTMA-Cu-6, P-TTMA-Cu-5, P-TTMA-Cu-4, P-TTMA-Cu-3, P-TTMA-Cu-2, and P-TTMA-Cu-1. This shows that different P-TTMA films all exhibit good corrosion inhibition performance for copper.

[0048] This embodiment uses a one-pot method. The total amount of copper bromide catalyst used in the entire experiment was 0.0446 g, with a molar mass of 224, yielding a molar amount of 0.1991 mmol. The reaction solution volume was 200 mL, resulting in a catalyst dosage of 9.96 × 10⁻⁶ g. -3 mmol·10mL -1

[0049] By calculating and comparing the amount of catalyst used in traditional ATRP and E-ATRP technologies, it was found that the amount of catalyst used in this experiment was less than that used in the traditional method. The results are shown in Table 1.

[0050] Comparative Example 1

[0051] This comparative example was prepared using the technical solution described in the patent application No. 2022115225303. This patent combines atom transfer radical polymerization and click chemistry. Click chemistry prepares monomers containing triazole functional groups, and atom transfer radical polymerization technology polymerizes the monomers containing triazole rings, thereby completing the preparation of triazole corrosion inhibitors.

[0052] The specific process is as follows: Using 1M propargyl acrylate and p-toluenesulfonyl azide as raw materials, 0.1mM cuprous thiophene-2-carboxylate (CuTc) as catalyst, and toluene as solvent, polymerizable monomers were prepared via click chemistry. In atom transfer radical polymerization (ATRP) reaction, triazole corrosion inhibitors with different degrees of polymerization were prepared by controlling the concentration of the initiator, with 10mM CuBr selected as the catalyst. The chemical reaction was carried out at room temperature for 2–3 hours. The product was purified by rotary evaporation to obtain a polymerizable monomer containing a triazole ring. Atom transfer radical polymerization was performed in a vacuum glove box, with the reagents loaded, and the polymerization reaction was carried out in a constant-temperature shaker for 8 hours at a reaction temperature of 60℃. The specific steps are as follows:

[0053] Using the experimental setup described above, the preparation method of the novel triazole corrosion-inhibiting polymer film on the copper surface is as follows:

[0054] (1) The copper samples were polished with sandpaper of 800, 1200 and 2000 grit respectively to obtain a smooth surface. A circular copper sample with a diameter of 15 mm and a thickness of 3 mm was used as a sampling piece for surface characterization and electrochemical studies. The samples were rinsed with ethanol, acetone and deionized water respectively.

[0055] (2) Polish the copper sheet until smooth, dry it with purified nitrogen gas, and soak it in 2 mol / L sodium hydroxide solution overnight to generate more monovalent copper ions on the copper surface. Rinse the copper sheet clean and dry it for later use. In a vacuum glove box, take 10 mL of tetrahydrofuran solution, 5 mmol of monomer, 0.05 mmol of ethyl 2-bromoisobutyrate, 0.2 mmol of pyridine, 0.1 mmol of ascorbic acid, and 0.1 mmol of cuprous chloride into a reaction flask, seal it with a sealing strip, and place it on a 60°C constant temperature shaker for surface-initiated atom transfer radical polymerization for 8 h. After the polymerization reaction is completed, put the polished copper sheet into the reaction flask for assembly. The assembly time is 2 h and the temperature is 25°C.

[0056] (3) Take out the assembled copper sheet, rinse it with ethanol, acetone and deionized water respectively and dry it. The surface of the copper sheet is covered with a layer of triazole corrosion inhibitor polymer film.

[0057] Comparative Example 2

[0058] This comparative example was prepared using the technical solution described in the patent application No. 2023107640277. This patent uses surface-initiated atom transfer radical polymerization technology to in-situ prepare a triazole corrosion-inhibiting polymer film on the copper surface.

[0059] The specific process is as follows:

[0060] A polymerizable monomer containing a triazole ring (TTMA) was prepared using 1M propargyl acrylate and 1M p-toluenesulfonyl azide as raw materials, 0.1mM cuprous thiophene-2-carboxylate (CuTc) as catalyst, and toluene as solvent. The chemical reaction was carried out at room temperature for 3 hours. The product was then purified by rotary evaporation (petroleum ether:ethyl acetate (PE:EA) = 6:1) to obtain a polymerizable monomer (TTMA) containing a triazole ring.

[0061] A copper sheet with a diameter of 15mm and a thickness of 2mm was used as the working electrode. The copper sheet was polished in sequence with 600 grit, 1000 grit, 1500 grit and 2000 grit, and then cleaned in sequence with deionized water, ethanol and deionized water, and dried with nitrogen gas for later use.

[0062] The pretreated copper sheet was reacted in a 0.08 wt.% THF solution with EBPA for 18 hours, and then washed with deionized water, ethanol, and deionized water in sequence, and dried with nitrogen.

[0063] Under an inert atmosphere, a copper sheet immobilized with an initiator was placed in a reaction flask with 5 mM monomer, 0.1 mM CuBr, 0.2 mM Me6TREN, and 10 ml THF. The flask was sealed with sealant and reacted at room temperature for 48 h. After the polymerization reaction was complete, the copper sheet was removed and washed sequentially with deionized water, ethanol, and then deionized water. It was then placed in a vacuum drying oven and vacuum dried at 60 °C for 12 h, resulting in a triazole corrosion-inhibiting polymer film coating the copper surface.

[0064] Table 1. Catalysts and their dosages in Example 1 and Comparative Examples 1-2

[0065] Example 1 <![CDATA[CuBr2,9.96×10 -3 ]]> Comparative Example 1 CuTc, 0.100; CuCl, 10.000 Comparative Example 2 CuTc, 0.100; CuBr, 10.000

[0066] As shown in Table 1, Example 1 requires only one catalyst, and the amount of catalyst used is significantly less than that in Comparative Examples 1 and 2. This is because the click chemistry reaction and the polymerization reaction have the same Cu(I) catalytic system, and the click chemistry reaction and the polymerization reaction can be carried out simultaneously through a "one-pot" method. In Comparative Examples 1 and 2, the reaction is catalyzed by directly adding Cu(I). In this example, under electrochemical control, Cu(II) is reduced to Cu(I) to catalyze the click chemistry and ATRP reactions. Since the catalyst does not participate in the reaction, Cu(I) is unstable, and the reaction is carried out in the air, Cu(I) is oxidized to Cu(II) during contact with oxygen. This process reduces the amount of catalyst used.

[0067] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization, characterized in that, Includes the following steps: Step 1: Add the solution containing propyne acrylate, p-toluenesulfonyl azide, catalyst, ligand and potassium bromide to the reactor; Step 2: Immerse the pretreated copper sheet in the initiator solution to allow the initiator to assemble on the surface of the copper sheet. After washing, you will get a copper sheet with the initiator assembled on its surface. Step 3: Place the copper sheet with the initiator assembled on its surface into the reactor and carry out the reaction fully under the mediation of electrochemistry, so that the click chemical reaction and the polymerization reaction occur simultaneously. The reaction is carried out under normal temperature and pressure conditions without the need for deoxygenation. After the copper sheet is taken out, washed and dried, a layer of triazole corrosion-inhibiting polymer film is coated on the surface of the copper sheet. The molar ratio of propyne acrylate, p-toluenesulfonyl azide, and catalyst is 900–1000:450–500:1; The catalyst is copper bromide; The potassium bromide is a supporting electrolyte used to improve the conductivity of the solution and does not participate in electrochemical reactions. The ligand is tris(2-(dimethylazo)ethyl)amine; The solution used to dissolve propyne acrylate, p-toluenesulfonyl azide, the catalyst, the ligand, and potassium bromide is an aqueous ethanol solution, wherein the volume ratio of ethanol to water in the aqueous ethanol solution is 0.5 to 2:

1.

2. The method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization according to claim 1, characterized in that, The copper sheet pretreatment steps are as follows: polish the copper sheet with 800, 1200, 1500 and 2000 grit sandpaper in sequence, and then rinse it clean with deionized water, anhydrous ethanol and deionized water.

3. The method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization according to claim 1, characterized in that, The initiator solution is an aqueous solution of ethanol containing 2-bromoisobutyric acid 2-hydroxyethyl ester.

4. The method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization according to claim 3, characterized in that, The volume ratio of anhydrous ethanol to water in the ethanol-water solution is 3 to 5:

1.

5. The method for preparing a triazole corrosion-inhibiting polymer film on a copper surface by in-situ initiation of electrochemically mediated atom transfer radical polymerization according to claim 1, characterized in that, In step three, the reaction time is 1 to 7 hours.

6. A triazole corrosion-inhibiting polymeric film, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 5.

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