Antioxidant copper conductor material and preparation method thereof

Abstract

The invention discloses an antioxidant copper conductor material and a preparation method thereof, and belongs to the technical field of copper conductor materials, and the preparation method comprises the following steps: S1, mixing absolute ethyl alcohol, deionized water and a silane-based Schiff base compound, stirring for 1 hour at 40 DEG C, adding conductive polyaniline, stirring for 2-4 hours while keeping the temperature, then adding cationic acrylic emulsion and a polyvinyl alcohol-based auxiliary component, and stirring for 2-4 hours while keeping the temperature; continuously stirring for 20 to 40 minutes to obtain an antioxidant solution; and S2, drawing the annealed copper wire to pass through an anti-oxidation liquid, drying at 80-100 DEG C for 3-5 minutes, and rolling, the anti-oxidation liquid forms a protective film on the surface of an annealed copper wire, the contact probability of oxygen and the copper wire is reduced, contact of a corrosion medium and a copper conductor is hindered, the copper conductor is endowed with good anti-oxidation and corrosion-resistant performance, in addition, compared with other protective films, the protective film has good conductivity, and the service life of the copper wire is prolonged. The adverse effect of the protective film on the performance of the copper conductor wire can be weakened.

Description

Technical Field

[0001] The invention belongs to the technical field of copper conductor materials, and in particular relates to an anti-oxidation copper conductor material and a preparation method thereof. Background Art

[0002] With the scarcity of natural resources and the increasing environmental problems, countries have been vigorously advocating energy conservation and emission reduction in order to combat climate change and promote green development. Against this background, the new energy industry, especially new energy vehicles, has developed rapidly. However, one of the main bottlenecks in the development of new energy vehicles is the charging problem. The charging effect and power transmission stability of new energy vehicles are closely related to the mechanical and electrical properties of the charging cable. At present, the cables required for charging mainly use pure copper conductor materials with good conductivity as cable cores, and the forming process of copper conductors is mainly achieved through drawing, annealing and other processes. However, the surface of metal copper is easy to react chemically with oxygen in humid air to generate Cu2(0H)2C03, that is, verdigris. Usually, the copper oxide surface in cable manufacturers is mostly black. The oxide generated on the surface of copper conductors increases the conductor resistance and increases the temperature, which shortens the service life of the wires. It is the existence of copper conductor surface oxidation that troubles many cable industries.

[0003] In order to prevent the oxidation of copper conductors, the existing technology generally performs anti-oxidation treatment during the processing process or performs anti-oxidation treatment on the finished product after the processing is completed. Among them, the anti-oxidation treatment of the finished product can exert a long-term anti-oxidation effect and is widely used. However, the antioxidant liquid used is generally composed of corrosion inhibitors and film-forming resins, which form a protective film on the surface of the copper busbar. This film will increase the resistance, thereby reducing the overall conductivity and affecting its use effect. Summary of the invention

[0004] The object of the present invention is to provide an anti-oxidation copper conductor material and a preparation method thereof, so as to solve the problem that the anti-oxidation performance and electrical conductivity of the existing copper conductor materials cannot be taken into account at the same time.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing an oxidation-resistant copper conductor material comprises the following steps:

[0007] S1. Mix anhydrous ethanol, deionized water and silane Schiff base compound, stir at 40°C for 1 hour, add conductive polyaniline, keep stirring for 2-4 hours, then add cationic acrylic emulsion and polyvinyl alcohol-based auxiliary components, continue stirring for 20-40 minutes, and obtain an antioxidant solution;

[0008] S2. The annealed copper wire is drawn through an antioxidant solution, then dried at 80-100° C. for 3-5 minutes, and rolled up to obtain an antioxidant copper conductor material.

[0009] Furthermore, the antioxidant liquid comprises components in the following parts by weight:

[0010] 25 parts of cationic acrylic emulsion, 10 parts of silane-based Schiff base compound, 2.5 parts of polyvinyl alcohol-based auxiliary component, 5 - 10 parts of conductive polyaniline, 60 - 70 parts of absolute ethanol, and 30 - 40 parts of deionized water.

[0011] In the preparation process of the antioxidant liquid of the present invention, first, the silane-based Schiff base compound is mixed with absolute ethanol and deionized water to obtain a hydrolysis solution of the silane-based Schiff base compound. Then, conductive polyaniline is added, and the modification effect of the silane-based Schiff base compound is utilized to improve the dispersibility of conductive polyaniline in the matrix. Finally, cationic acrylic emulsion and polyvinyl alcohol-based auxiliary component are added to obtain the antioxidant liquid. During the film-forming process of the antioxidant liquid, a cross-linking reaction occurs between the cationic acrylic emulsion and the silanol generated by the hydrolysis of the silane-based Schiff base compound to form the skeleton of the protective film. The conductive polyaniline forms a three-dimensional conductive network in the film layer, endowing the film layer with good conductivity. The carboxyl group in the polyvinyl alcohol-based auxiliary component can form a hydrogen bond with the carbonyl group in the cationic acrylic emulsion to improve the stability of the film layer. In addition, the long-chain alkyl group carried on the molecular chain of the polyvinyl alcohol-based auxiliary component has a hydrophobic effect, which can enhance the corrosion resistance of the film layer.

[0012] Furthermore, the preparation method of the silane-based Schiff base compound comprises the following steps:

[0013] The terminal amino silane and anhydrous sodium sulfate are added to absolute ethanol, and stirred at 25°C under nitrogen protection for 15 - 30 min. Then, salicylaldehyde is slowly added dropwise. After the addition is complete, the reaction is refluxed for 3 h under nitrogen protection. After the reaction is completed, sodium sulfate is removed by hot filtration, and the filtrate is distilled under reduced pressure to obtain the silane-based Schiff base compound.

[0014] Furthermore, the molar ratio of the terminal amino silane to salicylaldehyde is 2:2.5 - 3. Using the terminal amino silane and salicylaldehyde as raw materials, the silane-based Schiff base compound is obtained through the condensation reaction between the amino group and the aldehyde group.

[0015] Furthermore, the terminal amino silane is at least one of 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, and N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane.

[0016] Furthermore, the dropping rate is 1 - 3 drops / second.

[0017] Furthermore, the preparation method of the polyvinyl alcohol-based auxiliary component comprises the following steps:

[0018] Heat polyvinyl alcohol and dissolve it in dry dimethyl sulfoxide, then transfer it to a flask. Add succinic anhydride and triethylamine to the flask, stir and react at room temperature for 24 h. Then add EDC·HCl and NHS, continue stirring for 0.5 h. After that, add long-chain alkylamine and continue stirring for 24 h. After the reaction is completed, pour the reaction product into acetone for precipitation, filter, and place the filter cake in a vacuum dryer at 60 °C for 24 h to obtain the polyvinyl alcohol-based auxiliary component.

[0019] Furthermore, the dosage ratio of polyvinyl alcohol, dry dimethyl sulfoxide, succinic anhydride, triethylamine, EDC·HCl [1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride], NHS (N-hydroxysuccinimide), and long-chain alkylamine is 4.4 g: 150 - 200 mL: 0.5 g: 0.1 - 0.2 g: 0.96 g: 0.56 g: 5 - 8 mmol. First, carboxylate polyvinyl alcohol with succinic anhydride, and then carry out an amide reaction with long-chain alkylamine to obtain the polyvinyl alcohol-based auxiliary component.

[0020] Furthermore, the long-chain alkylamine is selected from at least one of dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine.

[0021] Furthermore, the polyvinyl alcohol is PVA1799 with a degree of polymerization of 1700 and a degree of alcoholysis of 99%.

[0022] Furthermore, the cationic acrylic emulsion is cationic acrylic emulsion 6306 with a solid content of 35% and a pH value of 6.0.

[0023] Furthermore, the annealed copper wire is prepared through the following steps:

[0024] Perform wire drawing on the finished rough copper wire to obtain a copper wire of the required size. Then, carry out annealing treatment using an inductive heat treatment tunnel furnace at an annealing temperature of 350 - 550 °C for an annealing time of 50 - 70 min, and then cool it to room temperature with the furnace to obtain the annealed copper wire.

[0025] An antioxidant copper conductor material is prepared by the above preparation method.

[0026] The beneficial effects of the present invention:

[0027] Aiming at the problem that the antioxidant performance and electrical conductivity of existing copper conductor materials cannot be taken into account at the same time, the present invention provides an antioxidant copper conductor material and a preparation method thereof. Cationic acrylic emulsion, silane Schiff base compound, polyvinyl alcohol-based auxiliary component, conductive polyaniline, anhydrous ethanol and deionized water are used as raw materials to prepare an antioxidant liquid, and a protective film is formed on the surface of the annealed copper wire to reduce the contact probability between oxygen and the copper wire, hinder the contact between the corrosive medium and the copper conductor, and give the copper conductor good antioxidant and corrosion resistance. In addition, compared with other protective films, the protective film has good electrical conductivity and can reduce the adverse effect of the protective film on the performance of the copper conductor wire.

[0028] The present invention uses a silyl Schiff base compound as an additive. Compared with a conventional coupling agent, the silyl Schiff base compound has a good surface modification effect and its imine characteristic group (-RC=N-) reacts chemically with the copper surface to form a chemical adsorption layer. The adsorption layer can effectively prevent further oxidation and corrosion of the copper surface. In addition, the rigid conjugated skeleton (the combination of an aromatic ring and an imine bond) on the molecular chain can form π-π stacking with the benzene ring and quinone structure of polyaniline, promote more orderly arrangement of the polyaniline molecular chain, reduce chain bond defects, thereby reducing electron transmission resistance and improving the conductivity of the protective film.

[0029] The present invention controls the order of adding materials so that the partial hydrolysis products of the silyl Schiff base compound are first combined with the conductive polyaniline, thereby improving the dispersibility of the conductive polyaniline in the base material, and the remaining hydrolysis products are cross-linked with the cationic acrylic emulsion to form a film, thereby obtaining a high-performance protective film. If the conductive polyaniline and the cationic acrylic emulsion are added to the hydrolyzate of the silyl Schiff base compound at the same time, there is a competitive reaction between the two, which will lead to insufficient surface modification of the conductive polyaniline, reduced dispersibility in the matrix, and significantly affecting the corrosion resistance and conductivity of the protective film. DETAILED DESCRIPTION

[0030] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. 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.

[0031] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, a~b (i.e. a and b), a~c, b~c, or a~b~c, where a, b, c can be single or multiple, respectively.

[0032] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a", "the", and "said" used in the embodiments of the present application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0033] It should be understood that in various embodiments of the present application, the magnitude of the sequence numbers of the respective processes does not mean the order of execution. Some or all of the steps may be executed in parallel or sequentially. The execution order of the respective processes should be determined by their functions and internal logics and should not constitute any limitation to the implementation process of the embodiments of the present application.

[0034] The weight of the relevant components mentioned in the specification of the embodiments of the present application not only can refer to the specific content of each component, but also can represent the proportional relationship of the weights between the components. Therefore, as long as the content of the relevant components in the specification of the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application can be mass units well-known in the chemical engineering field such as μg, mg, g, kg, etc.

[0035] Unless otherwise defined, all the technical terms used hereinafter have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present invention.

[0036] Unless otherwise specifically stated, all kinds of raw materials, reagents, instruments, equipment, etc. used in the present application can be obtained through market purchase or can be prepared by existing methods.

[0037] The technical solutions of the present application will be described below through specific examples and comparative examples.

[0038] Preparation Example 1

[0039] A preparation method of a polyvinyl alcohol-based auxiliary component, comprising the following steps:

[0040] 4.4 g of polyvinyl alcohol was heated and dissolved in 150 mL of dry dimethyl sulfoxide and then transferred to a flask. The polyvinyl alcohol was PVA1799 with a degree of polymerization of 1700 and a degree of alcoholysis of 99%. 0.5 g of succinic anhydride and 0.1 g of triethylamine were added to the flask, and the mixture was stirred at room temperature for 24 h. Then 0.96 g of EDC·HCl and 0.56 g of NHS were added, and stirring was continued for 0.5 h. Then 5 mmol of dodecylamine was added, and stirring was continued for 24 h. After the reaction was completed, the reaction product was poured into acetone for precipitation, filtered, and the filter cake was placed in a vacuum dryer at 60 °C for 24 h to obtain the polyvinyl alcohol-based auxiliary component.

[0041] Preparation Example 2

[0042] A preparation method of a polyvinyl alcohol-based auxiliary component, comprising the following steps:

[0043] Heat 4.4 g of polyvinyl alcohol and dissolve it in 180 mL of dry dimethyl sulfoxide, then transfer it to a flask. The polyvinyl alcohol is PVA1799 with a degree of polymerization of 1700 and a degree of alcoholysis of 99%. Add 0.5 g of succinic anhydride and 0.2 g of triethylamine to the flask, stir and react at room temperature for 24 h. Then add 0.96 g of EDC·HCl and 0.56 g of NHS, continue stirring for 0.5 h. Then add 7 mmol of hexadecylamine and continue stirring for 24 h. After the reaction is completed, pour the reaction product into acetone for precipitation, filter, and place the filter cake in a vacuum dryer at 60 °C for 24 h to obtain the polyvinyl alcohol-based auxiliary component.

[0044] Preparation Example 3

[0045] A preparation method of a polyvinyl alcohol-based auxiliary component, comprising the following steps:

[0046] Heat 4.4 g of polyvinyl alcohol and dissolve it in 200 mL of dry dimethyl sulfoxide, then transfer it to a flask. The polyvinyl alcohol is PVA1799 with a degree of polymerization of 1700 and a degree of alcoholysis of 99%. Add 0.5 g of succinic anhydride and 0.2 g of triethylamine to the flask, stir and react at room temperature for 24 h. Then add 0.96 g of EDC·HCl and 0.56 g of NHS, continue stirring for 0.5 h. Then add 8 mmol of octadecylamine and continue stirring for 24 h. After the reaction is completed, pour the reaction product into acetone for precipitation, filter, and place the filter cake in a vacuum dryer at 60 °C for 24 h to obtain the polyvinyl alcohol-based auxiliary component.

[0047] Example 1

[0048] A preparation method of an antioxidant copper conductor material, comprising the following steps:

[0049] S1. Add absolute ethanol, deionized water and a silane-based Schiff base compound to a mixing tank, stir at 40 °C for 1 h, add conductive polyaniline, keep stirring for 2 h, then add a cationic acrylic emulsion and a polyvinyl alcohol-based auxiliary component, and continue stirring for 20 min to obtain an antioxidant liquid;

[0050] S2. Draw the annealed copper wire through the antioxidant liquid, then dry it at 80 °C for 3 min, and wind it up to obtain the antioxidant copper conductor material.

[0051] The antioxidant liquid comprises the following components in parts by weight:

[0052] 25 parts of cationic acrylic emulsion, 10 parts of silane-based Schiff base compound, 2.5 parts of the polyvinyl alcohol-based auxiliary component of Preparation Example 1, 5 parts of conductive polyaniline, 60 parts of absolute ethanol, and 30 parts of deionized water.

[0053] The preparation method of the silyl Schiff base compound comprises the following steps:

[0054] 25 mmol of 3-aminopropyltrimethoxysilane and 2.0 g of anhydrous sodium sulfate are added to 50 mL of absolute ethanol. Under nitrogen protection at 25 °C, it is stirred for 15 min, and then 30 mmol of salicylaldehyde is slowly added dropwise at a rate of 1 drop per second. After the addition is completed, it is refluxed and reacted for 3 h under nitrogen protection. After the reaction is completed, sodium sulfate is removed by hot filtration while it is hot, and the filtrate is distilled under reduced pressure to obtain the silyl Schiff base compound.

[0055] The cationic acrylic emulsion is cationic acrylic emulsion 6306, with a solid content of 35% and a pH value of 6.0.

[0056] The annealed copper wire is obtained through the following steps:

[0057] The finished rough copper wire is drawn to obtain a copper wire with the required size, and then it is annealed using an inductive heat treatment tunnel furnace at an annealing temperature of 350 °C for 70 min, and then cooled to room temperature with the furnace to obtain the annealed copper wire.

[0058] Example 2

[0059] A preparation method of an antioxidant copper conductor material comprises the following steps:

[0060] S1. Absolute ethanol, deionized water and the silyl Schiff base compound are added to a mixing tank, stirred at 40 °C for 1 h, conductive polyaniline is added, and it is kept warm and stirred for 3 h. Then the cationic acrylic emulsion and the polyvinyl alcohol-based auxiliary component are added, and stirring is continued for 30 min to obtain an antioxidant liquid;

[0061] S2. The annealed copper wire is drawn through the antioxidant liquid, then dried at 90 °C for 4 min, and wound up to obtain the antioxidant copper conductor material.

[0062] The antioxidant liquid comprises the following components in parts by weight:

[0063] 25 parts of cationic acrylic emulsion, 10 parts of silyl Schiff base compound, 2.5 parts of polyvinyl alcohol-based auxiliary component of Preparation Example 1, 8 parts of conductive polyaniline, 65 parts of absolute ethanol, and 35 parts of deionized water.

[0064] The preparation method of the silyl Schiff base compound comprises the following steps:

[0065] Add 25 mmol of 3-aminopropyltrimethoxysilane and 2.0 g of anhydrous sodium sulfate to 50 mL of absolute ethanol. Stir at 25 °C under nitrogen protection for 30 min, then slowly add 30 mmol of salicylaldehyde dropwise at a rate of 3 drops per second. After the addition is complete, reflux and react for 3 h under nitrogen protection. After the reaction is completed, filter off the sodium sulfate while it is hot, and distill the filtrate under reduced pressure to obtain the silyl Schiff base compound.

[0066] The cationic acrylic emulsion is cationic acrylic emulsion 6306, with a solid content of 35% and a pH value of 6.0.

[0067] The annealed copper wire is prepared by the following steps:

[0068] Perform wire drawing on the finished crude copper wire to obtain a copper wire of the required size, then perform annealing treatment using an inductive heat treatment tunnel furnace at an annealing temperature of 550 °C for 50 min, and then cool it to room temperature in the furnace to obtain the annealed copper wire.

[0069] Example 3

[0070] A preparation method of an antioxidant copper conductor material includes the following steps:

[0071] S1. Add absolute ethanol, deionized water, and the silyl Schiff base compound to a mixing tank, stir at 40 °C for 1 h, add conductive polyaniline, keep warm and stir for 4 h, then add the cationic acrylic emulsion and the polyvinyl alcohol-based auxiliary component, and continue to stir for 40 min to obtain the antioxidant liquid;

[0072] S2. Draw the annealed copper wire through the antioxidant liquid, then dry it at 100 °C for 5 min, and wind it up to obtain the antioxidant copper conductor material.

[0073] The antioxidant liquid includes the following components in parts by weight:

[0074] 25 parts of cationic acrylic emulsion, 10 parts of silyl Schiff base compound, 2.5 parts of the polyvinyl alcohol-based auxiliary component of Preparation Example 1, 10 parts of conductive polyaniline, 70 parts of absolute ethanol, and 40 parts of deionized water.

[0075] The preparation method of the silyl Schiff base compound includes the following steps:

[0076] Add 25 mmol of 3-aminopropyltrimethoxysilane and 2.0 g of anhydrous sodium sulfate to 50 mL of absolute ethanol. Stir at 25 °C under nitrogen protection for 30 min, then slowly add 30 mmol of salicylaldehyde dropwise at a rate of 3 drops per second. After the addition is complete, reflux and react for 3 h under nitrogen protection. After the reaction is completed, filter off the sodium sulfate while it is hot, and distill the filtrate under reduced pressure to obtain the silyl Schiff base compound.

[0077] The cationic acrylic emulsion is cationic acrylic emulsion 6306, with a solid content of 35% and a pH value of 6.0.

[0078] The annealed copper wire is prepared through the following steps:

[0079] The finished thick copper wire is drawn to obtain a copper wire of the required size, and then annealed using an inductive heat treatment tunnel furnace at an annealing temperature of 550 °C for 20 minutes, and then cooled to room temperature with the furnace to obtain the annealed copper wire.

[0080] Example 4

[0081] A preparation method of an antioxidant copper conductor material, compared with Example 1, the difference is only that the "polyvinyl alcohol-based auxiliary component" in Example 1 is replaced with the substance in Preparation Example 2.

[0082] Example 5

[0083] A preparation method of an antioxidant copper conductor material, compared with Example 1, the difference is only that the "polyvinyl alcohol-based auxiliary component" in Example 1 is replaced with the substance in Preparation Example 3.

[0084] Example 6

[0085] A preparation method of an antioxidant copper conductor material, compared with Example 1, the difference is only that the "3-aminopropyl-trimethoxysilane" in Example 1 is replaced with an equal mass of "3-aminopropyl-triethoxysilane".

[0086] Example 7

[0087] A preparation method of an antioxidant copper conductor material, compared with Example 1, the difference is only that the "3-aminopropyl-trimethoxysilane" in Example 1 is replaced with an equal mass of "N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane".

[0088] Example 8

[0089] A preparation method of an antioxidant copper conductor material, compared with Example 1, the difference is only that the dosage of conductive polyaniline in Example 1 is adjusted from "5 parts by weight" to "8 parts by weight".

[0090] Comparative Example 1

[0091] A preparation method of an antioxidant copper conductor material, compared with Example 1, the difference is only that the "silyl Schiff base compound" in Example 1 is replaced with an equal mass of "3-aminopropyl-trimethoxysilane".

[0092] Comparative Example 2

[0093] A preparation method of an antioxidant copper conductor material. Compared with Example 1, the only difference is that the "polyvinyl alcohol-based auxiliary component" in Example 1 is replaced with an equal mass of "polyvinyl alcohol". In this comparative example, the polyvinyl alcohol is PVA1799, with a polymerization degree of 1700 and a degree of alcoholysis of 99%.

[0094] Comparative Example 3

[0095] A preparation method of an antioxidant copper conductor material. Compared with Example 1, the only difference is the different feeding order during the preparation of the antioxidant solution. The preparation process of the antioxidant solution in this comparative example is as follows:

[0096] Add absolute ethanol, deionized water, and a silane-based Schiff base compound into a mixing tank, stir at 40°C for 1 h, add conductive polyaniline and a cationic acrylic emulsion, keep warm and stir for 2 h, then add the polyvinyl alcohol-based auxiliary component, and continue to stir for 20 min to obtain the antioxidant solution.

[0097] Perform performance tests on the copper conductor materials obtained from Example 1 - Example 8 and Comparative Example 1 - Comparative Example 3. The test process is as follows:

[0098] Conductivity: Test the maximum resistance at 20°C with reference to the measurement method disclosed in GB / T3956 - 2008 Conductors of Cables;

[0099] Antioxidation property: Place the copper conductor materials of each group in a constant temperature and humidity chamber. The test conditions are 50°C, and the humidity in the chamber is controlled at 70%. After 28 days, test the maximum resistance of the conductor materials at 20°C;

[0100] Corrosion resistance: Immerse the copper conductor materials of each group in a 0.1 M sodium hydroxide solution for 12 h, and observe whether the surface of the copper conductor materials is mottled and whether the color changes.

[0101] The results are shown in Table 1:

[0102] Table 1

[0103]

[0104] As can be seen from the data recorded in Table 1, the maximum resistance of the copper conductor materials obtained in Examples 1-8 at 20 °C is 1.21-1.34 Ω / km, which is significantly lower than that of the copper conductor materials obtained in Comparative Example 2 and Comparative Example 3, indicating that the copper conductor materials prepared by the present invention have good electrical conductivity. The maximum resistance of the copper conductor materials obtained in Examples 1-8 slightly increases at 50 °C, with a humidity of 70%, and after 28 days of oxidation at 20 °C. The maximum resistance of the copper conductor materials obtained in Comparative Example 1, Comparative Example 2, and Comparative Example 3 significantly increases after oxidation at 20 °C, indicating that the copper conductor materials prepared by the present invention have good oxidation resistance. Moreover, there is no change on the surface of the copper conductor materials obtained in Examples 1-8 after 12 h in 0.1 M sodium hydroxide solution, while mottling and color change appear on the surface of the copper conductor materials obtained in Comparative Example 1-Comparative Example 3, indicating that the copper conductor materials prepared by the present invention have good corrosion resistance.

[0105] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0106] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of an antioxidant copper conductor material, characterized in that, It includes the following steps: S1. Mix absolute ethanol, deionized water and silane-based Schiff base compound, stir at 40 °C for 1 h, add conductive polyaniline, keep warm and stir for 2 - 4 h, then add cationic acrylic emulsion and polyvinyl alcohol-based auxiliary component, and continue to stir for 20 - 40 min to obtain an antioxidant liquid; S2. Draw the annealed copper wire through the antioxidant liquid, dry it at 80 - 100 °C for 3 - 5 min, and wind it up to obtain an antioxidant copper conductor material; The antioxidant liquid comprises the following components in parts by weight: 25 parts of cationic acrylic emulsion, 10 parts of silane-based Schiff base compound, 2.5 parts of polyvinyl alcohol-based auxiliary component, 5 - 10 parts of conductive polyaniline, 60 - 70 parts of absolute ethanol, and 30 - 40 parts of deionized water.

2. The preparation method of an antioxidant copper conductor material according to claim 1, wherein, The preparation method of the silane-based Schiff base compound includes the following steps: Add aminoalkyl silane and anhydrous sodium sulfate into absolute ethanol, stir at 25 °C under nitrogen protection for 15 - 30 min, slowly dropwise add salicylaldehyde, after the addition is complete, reflux and react for 3 h under nitrogen protection, after the reaction ends, filter while it is hot, and distill the filtrate under reduced pressure to obtain the silane-based Schiff base compound.

3. The preparation method of an antioxidant copper conductor material according to claim 2, wherein, The molar ratio of aminoalkyl silane to salicylaldehyde is 2:2.5 - 3.

4. The preparation method of an antioxidant copper conductor material according to claim 2, wherein The aminoalkyl silane is at least one of 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane and N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane.

5. The preparation method of an antioxidant copper conductor material according to claim 1, characterized in that, The preparation method of the polyvinyl alcohol-based auxiliary component includes the following steps: Heat and dissolve polyvinyl alcohol in dry dimethyl sulfoxide and then transfer it to a flask, add succinic anhydride and triethylamine to the flask, stir and react at room temperature for 24 h, then add EDC·HCl and NHS, continue to stir for 0.5 h, then add long-chain alkylamine, continue to stir for 24 h, after the reaction ends, pour the reaction product into acetone for precipitation, filter, and place the filter cake in a vacuum dryer at 60 °C for 24 h to obtain the polyvinyl alcohol-based auxiliary component.

6. The preparation method of an antioxidant copper conductor material according to claim 5, characterized in that, The dosage ratio of polyvinyl alcohol, dry dimethyl sulfoxide, succinic anhydride, triethylamine, EDC·HCl, NHS and long-chain alkylamine is 4.4 g:150 - 200 mL:0.5 g:0.1 - 0.2 g:0.96 g:0.56 g:5 - 8 mmol.

7. The preparation method of an antioxidant copper conductor material according to claim 5, characterized in that, The long-chain alkylamine is selected from at least one of dodecylamine, tetradecylamine, hexadecylamine and octadecylamine.

8. The preparation method of an antioxidant copper conductor material according to claim 1, characterized in that, The polyvinyl alcohol is PVA1799, with a polymerization degree of 1700 and a degree of alcoholysis of 99%.

9. The preparation method of an antioxidant copper conductor material according to claim 1, characterized in that, The cationic acrylic emulsion is cationic acrylic emulsion 6306, with a solid content of 35% and a pH value of 6.

0.

10. An antioxidant copper conductor material, characterized in that, Prepared by the preparation method according to any one of claims 1 - 9.

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