Drawing oil applied to the drawing of aluminum-based fine wires and its preparation method

Abstract

The present invention discloses a wire drawing oil applied to the drawing of aluminum-based fine wires and a preparation method thereof, belonging to the technical field of wire drawing oil processing. Specifically, it includes: a modifier, a fluorinated polysiloxane modified with alcohol ammonia, a thickener, an additive aid, and a base oil. In the present invention, after the base oil is modified by a modifier containing imidazole ionic salt, the modified base oil is further enhanced by using a fluorinated polysiloxane modified with alcohol ammonia and a thickener, which not only effectively increases the extreme pressure resistance and anti-wear performance of the wire drawing oil, but also reduces the wire breakage rate of drawing 0.1 mm aluminum-based fine wires and improves the production rate of aluminum-based fine wires.

Description

Technical Field

[0001] The present invention relates to the technical field of wire drawing oil processing, and particularly relates to a wire drawing oil applied to the drawing of aluminum-based fine wires and a preparation method thereof. Background Art

[0002] The manufacturing process of enameled wire consists of a series of different production processes. Among them, the wire drawing process is a very important process in the entire manufacturing process. Due to the very diverse specifications of enameled wire, during the manufacturing process, it is necessary to draw the conductor material into different sizes according to different requirements at any time. This drawing production process is the wire drawing production process. Wire drawing oil is the most important raw and auxiliary material in wire drawing production, playing roles such as lubrication, cleaning, cooling, and anti-oxidation during the drawing process, providing quality assurance for the semi-finished products after drawing. Therefore, the quality of wire drawing oil directly affects the stability of the wire drawing manufacturing process and the quality of the semi-finished products after drawing.

[0003] The wire drawing process can be divided into categories such as large drawing, medium drawing, small drawing, and micro drawing according to the type of wire drawing equipment and the size of the drawn aluminum wire. The currently commonly used aluminum-based wire drawing oil in the industry can be well applied to large drawing, medium drawing, and small drawing. Micro drawing is mostly defined as aluminum wire with a diameter of less than 0.18 mm. Traditional wire drawing oil has insufficient high-temperature stability. The wire drawing oil is prone to oxidation and decomposition at high temperatures generated during high-speed wire drawing, resulting in the rupture of the oil film, causing oxidation on the surface of the aluminum wire or local adhesive wear. Moreover, its extreme pressure and anti-wear performance are poor. Although sulfur / phosphorus-based additives can improve the extreme pressure performance, the aluminum sulfide film formed by the reaction of its active components on the aluminum surface is brittle and prone to peeling off after long-term use, exacerbating abrasive wear. In addition, it is difficult for lubricating wire drawing oil to form a continuous and uniform lubricating film in the sub-micron die gap, resulting in a high wire breakage rate of aluminum wire with a diameter of less than 0.1 mm, severely restricting the production rate and indirectly increasing the manufacturing cost. Summary of the Invention

[0004] The purpose of the present invention is to provide a wire drawing oil applied to the drawing of aluminum-based fine wires and a preparation method thereof, aiming to solve the technical problems in the prior art that the wire drawing oil for drawing aluminum-based fine wires has poor extreme pressure resistance, anti-wear performance, and surface lubrication performance, resulting in a high wire breakage rate in the drawing of aluminum-based fine wires and the need to further improve the production rate.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A wire drawing oil applied to the drawing of aluminum-based fine wires, comprising the following components by weight: 15 - 20 parts of a modifier, 10 - 13 parts of fluorinated polysiloxane modified with alcohol ammonia, 5 - 7 parts of a thickener, 3 - 5 parts of an additive aid, and 80 - 90 parts of a base oil;

[0006] The base oil is neopentyl polyol ester;

[0007] The modifier is composed of an imidazole solution, triethanolamine borate, and triethanolamine oleate soap in a weight ratio of 2:5:2. The imidazole solution is composed of imidazolium salt and isopropanol in a ratio of 2g:3mL.

[0008] Furthermore, the alcohol-amine modified fluorinated polysiloxane is obtained by the following steps:

[0009] A1. Stir and mix fluorinated polysiloxane, isopropanol, and 1,2-epoxy-5-hexene. Raise the temperature of the reaction system to 76 - 82 °C. Add a platinum catalyst to the reaction system and keep the reaction at a constant temperature for 5 - 6 h. After post-treatment, epoxidized fluorinated polysiloxane is obtained.

[0010] The synthesis reaction equation of epoxidized fluorinated polysiloxane is:

[0011]

[0012]

[0013] The synthesis reaction mechanism of epoxidized fluorinated polysiloxane is:

[0014] During the reaction process, under the action of the catalyst, the olefin on the 1,2-epoxy-5-hexene molecule undergoes an addition reaction with the silicon hydride on the fluorinated polysiloxane molecule, and an epoxy group is modified on the fluorinated polysiloxane molecule to prepare epoxidized fluorinated polysiloxane.

[0015] A2. Stir and mix epoxidized fluorinated polysiloxane, isopropanol, and N,N-bis(2-hydroxyethyl)ethylenediamine. Raise the temperature of the reaction system to 70 - 80 °C and keep the reaction at a constant temperature for 4 - 5 h. After post-treatment, alcohol-amine modified fluorinated polysiloxane is obtained.

[0016] The synthesis reaction equation of alcohol-amine modified fluorinated polysiloxane is:

[0017]

[0018] In the formula, R1 is:

[0019] The synthesis reaction mechanism of alcohol-amine modified fluorinated polysiloxane is:

[0020] During the reaction process, taking the amino group on the N,N-bis(2-hydroxyethyl)ethylenediamine molecule as the reaction active site, it undergoes ring-opening condensation with the epoxy group on the epoxidized fluorinated polysiloxane molecule at high temperature to form a polyhydroxy modification, and alcohol-amine modified fluorinated polysiloxane is prepared.

[0021] Further, in step A1, the dosage ratio of the fluorinated polysiloxane, isopropyl alcohol, 1,2-epoxy-5-hexene, and platinum catalyst is 5 g: 100 mL: 0.6 g: 0.02 g. The platinum catalyst is chloroplatinic acid. The post-treatment includes: after the reaction is completed, the temperature of the reaction system is kept at 76 - 82 °C, and the low-boiling substances are removed by reduced pressure distillation to obtain epoxidized fluorinated polysiloxane. In step A2, the dosage ratio of the epoxidized fluorinated polysiloxane, isopropyl alcohol, and N,N-bis(2-hydroxyethyl)ethylenediamine is 5 g: 10 mL: 1 g. The post-treatment includes: after the reaction is completed, the reaction system is kept at 70 - 80 °C, the low-boiling substances are removed by reduced pressure distillation, the temperature of the reaction system is lowered to room temperature, purified water is added to the reaction system, stirred and dispersed for 20 - 30 min, allowed to stand for liquid separation, the upper layer solution is washed 3 times with purified water, the upper layer solution is dried with anhydrous sodium sulfate for 4 h, and filtered to obtain alcohol-amine modified fluorinated polysiloxane.

[0022] Further, the preparation method of the fluorinated polysiloxane is as follows: D4, D3F, D4H, and 1,1,3,3-tetramethyldisiloxane are stirred and mixed, a catalyst is added to the reaction system, the temperature of the reaction system is raised to 70 - 80 °C, and the reaction is kept for 6 - 8 h, followed by post-treatment to obtain the fluorinated polysiloxane.

[0023] The synthesis reaction equation of the fluorinated polysiloxane is:

[0024]

[0025] The synthesis reaction mechanism of the fluorinated polysiloxane is:

[0026] During the reaction process, under the action of the catalyst, the ring-opening of the siloxane of D4, D3F, and D4H is initiated to form a linear polysiloxane chain, and the fluorine / hydrogen side groups are randomly distributed. 1,1,3,3-Tetramethyldisiloxane is used as a capping agent to limit the chain length, and the fluorinated polysiloxane containing fluorine and silicon hydride modification is prepared.

[0027] Further, the weight ratio of D4, D3F, D4H, 1,1,3,3-tetramethyldisiloxane, and acid catalyst is 6:4:3:1:0.3. The acid catalyst is 85 - 95 wt% sulfuric acid. The post-treatment includes: after the reaction is completed, the temperature of the reaction system is lowered to room temperature, 3 wt% aqueous sodium carbonate solution is added to the reaction system to adjust the system pH = 6 - 7, allowed to stand for liquid separation, the upper layer solution is washed 2 times with saturated sodium carbonate and then 3 times with purified water, the upper layer solution is dried with anhydrous sodium sulfate for 4 h, and filtered to obtain the fluorinated polysiloxane.

[0028] Further, the preparation method of the thickener is as follows: under the protection of an inert atmosphere, 4,4'-diaminodiphenylmethane, end-capping amine, and tetrahydrofuran are stirred and mixed, the temperature of the reaction system is raised to 40-50 °C, toluene diisocyanate is added to the reaction system, and the reaction is carried out under insulation for 60-80 min, followed by post-treatment to obtain the thickener.

[0029] The synthesis reaction equation of the thickener is:

[0030]

[0031] In the formula, R2 is: , , , , any one of

[0032] The synthesis reaction mechanism of the thickener is:

[0033] During the reaction, the amino group on the 4,4'-diaminodiphenylmethane molecule reacts with the isocyanate group on the toluene diisocyanate molecule to form a polyurethane molecule at the long-chain end. The end-capping amine acts as a chain capping terminator to limit chain growth, and the thickener is prepared.

[0034] Further, the dosage ratio of 4,4'-diaminodiphenylmethane, end-capping amine, and toluene diisocyanate is 5 mol: 2 mol: 6 mol, the dosage ratio of 4,4'-diaminodiphenylmethane and tetrahydrofuran is 1 g: 5 mL, the end-capping amine is ethyl 6-aminocaproate, and the post-treatment includes: after the reaction is completed, the reaction system is kept at 40-50 °C, and tetrahydrofuran is removed under reduced pressure to obtain the thickener.

[0035] Further, the preparation method of the imidazolium ion salt is as follows: 3,5-dihydroxybenzoic acid, sodium bicarbonate, and absolute ethanol are stirred and mixed until the system is dissolved, the temperature of the reaction system is raised to 40-50 °C, a solution of 1-butyl-3-methylimidazolium chloride is added dropwise to the reaction system, and after the addition is complete, the reaction is carried out at room temperature for 20-24 h, followed by post-treatment to obtain the imidazolium ion salt.

[0036] The synthesis reaction mechanism of the imidazolium ion salt is:

[0037] During the reaction, under the action of sodium bicarbonate, the carboxyl proton of 3,5-dihydroxybenzoic acid is neutralized to form a carboxylate salt, enhancing the nucleophilicity of the carboxylate group. The oxygen of the carboxylate group attacks the C2 position of 1-butyl-3-methylimidazolium chloride, and Cl - is replaced as a leaving group to form an imidazolium ion salt, and the by-product NaCl is generated.

[0038] Further, the dosage ratio of 3,5-dihydroxybenzoic acid, sodium bicarbonate and 1-butyl-3-methylimidazolium chloride is 1 mol: 1.2 mol: 1 mol, the dosage ratio of 3,5-dihydroxybenzoic acid and absolute ethanol is 1 g: 5 mL, the 1-butyl-3-methylimidazolium chloride solution is composed of 1-butyl-3-methylimidazolium chloride and absolute ethanol at 1 g: 2 mL, and the post-treatment includes: after the reaction is completed, the temperature of the reaction system is reduced to 5-10 °C, filtered by suction, and the filtrate is transferred to a rotary evaporator with a water bath temperature of 50-60 °C, and the low-boiling substances are removed under reduced pressure to obtain the imidazolium salt.

[0039] The present invention also provides a method for preparing a wire drawing oil applied to the drawing of aluminum-based fine wires, comprising the following steps:

[0040] S1. Mix a base oil and a modifier to obtain a modified base oil;

[0041] S2. Mix the fluorinated polysiloxane modified with alcohol ammonia, a thickener, an additive and the modified base oil evenly to obtain the wire drawing oil.

[0042] The present invention has the following beneficial effects:

[0043] 1. For the wire drawing oil for drawing aluminum-based fine wires of the present invention, by selecting neopentyl polyol ester as the base oil, it has a highly branched neopentyl structure, which endows it with high thermal stability, low pour point and high viscosity index. The branching reduces the crystallization tendency of ester molecules, ensuring low-temperature fluidity, and at the same time, the viscosity drops gently at high temperatures, adapting to the temperature fluctuations during the wire drawing process. The ester group forms a physical lubricating film on the aluminum surface through polar adsorption, reducing direct metal-to-metal contact. The imidazole cation in the modifier forms a dense organic film on the aluminum surface through electrostatic adsorption. The phenolic hydroxyl group of 3,5-dihydroxybenzoic acid binds to the aluminum oxide layer through hydrogen bonds or chemical bonds, enhancing the adsorption strength. The B-O bond in triethanolamine borate hydrolyzes under the action of frictional heat to generate boric acid, which reacts with the aluminum surface to form aluminum borate or boron oxide compound, reducing the friction coefficient. Moreover, the borate can also cooperate with the imidazole salt to form a composite lubricating film such as a B-N coordination bond, enhancing the high-temperature resistance of the film layer. The long-chain alkyl group (C18) of oleic acid soap is oriented in the oil phase to form a micelle structure, which helps to disperse the imidazole salt and borate, prevent agglomeration, and assist the uniform spreading of the lubricating film. The non-polar branches of neopentyl polyol ester provide the main lubricating phase, while the polar components of the modifier are enriched on the metal surface to form a gradient lubricating layer, adapting to the lubrication requirements at different pressure stages. After the weak adsorption film of the ester group is damaged at high temperatures, the imidazole salt and borate quickly fill the defects through chemical adsorption / reaction, realizing the dynamic repair of the lubricating film, reducing the wear scar diameter and the wire breakage rate.

[0044] 2. The wire drawing oil for drawing aluminum-based fine wires of the present invention has a thickener formed by polycondensation of 4,4'-diaminodiphenylmethane, ethyl 6-aminocaproate, and toluene diisocyanate to produce a polyurethane-type polymer. The rigid aromatic ring structure in its molecular structure enhances the rigidity and thermal stability of the molecular chain. The ethyl caproate chain segment imparts flexibility and stretchability, forming a block structure with alternating "hard segments - soft segments". The thickener molecules are bonded through hydrogen bonds to construct a three-dimensional physical crosslinking network. The rigid aromatic rings on the thickener molecular chain form a physical barrier under high pressure, hindering the direct contact of microprotrusions on the metal surface and delaying the occurrence of seizure. The flexible chain segments of the thickener are oriented along the sliding direction under the action of frictional shear force to form an oriented lubricating layer with a low coefficient of friction. Moreover, the thickener can jointly form a composite extreme pressure film with imidazole salts and borate esters in the modifier. The hydrogen bond crosslinking network of the thickener captures wear particles through hydrogen bonds to prevent secondary abrasive wear. Under the action of external force, the hydrogen bond network preferentially breaks and absorbs energy, reducing stress concentration and the wire breakage rate.

[0045] 3. The wire drawing oil for drawing aluminum-based fine wires of the present invention has an alcohol-amine modified fluorinated polysiloxane formed by the ring-opening reaction of N,N-bis(2-hydroxyethyl)ethylenediamine and epoxy group modified fluorinated polysiloxane to form polar branches containing hydroxyl and amino groups on the long polysiloxane molecular chain. The CF3 groups on the molecular chain form a low surface energy lubricating layer on the aluminum surface, reducing the tendency of metal adhesion. The flexibility of the Si-O-Si main chain absorbs impact energy through conformational changes, delaying the rupture of the extreme pressure film. The hydroxyl / amino groups enhance the adhesion of the boundary lubricating film through chemical adsorption. Moreover, the amino groups adsorb aluminum wear debris through electrostatic action. It cooperates with the thickener and the modified base oil to quickly clean aluminum powder, aluminum sludge, etc. generated during wire drawing from the surface of the wire and the wire drawing die during the wire drawing process, preventing their aggregation from causing wear, and further significantly reducing die jamming and wire breakage caused by the accumulation and residue of aluminum sludge, further enhancing the lubricating wire drawing performance of the wire drawing oil for aluminum wires, making it more suitable for the forming of aluminum-based fine wires. Detailed implementation manners

[0046] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0047] In this application, the neopentyl polyol ester is selected from Jining Huipeng Chemical Co., Ltd., with a CAS number of 65461-8945-7 and a hydroxyl value of 5 mgKOH / g;

[0048] In this application, D4 is octamethylcyclotetrasiloxane, with a CAS number of 556-67-2;

[0049] In this application, D3F is 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, with a CAS number of 2374-14-3;

[0050] In this application, D4H is 1,3,5,7-tetramethylcyclotetrasiloxane, with a CAS number of 2370-88-9;

[0051] In this application, the sulfurized fatty acid ester is selected from Jinzhou Chenghua New Materials Co., Ltd., with a CAS number of 68390-93-2 and a model number of T1015;

[0052] In this application, the monoalkenyl succinimide is selected from Jinzhou Chenghua New Materials Co., Ltd., with a model number of T-151, a kinematic viscosity (at 100 °C) of 178.5, and a total base number of 48 mg KOH / g;

[0053] In this application, the dodecanedioic acid has a CAS number of 693-23-2;

[0054] In this application, the triethanolamine borate has a CAS number of 206-003-5;

[0055] In this application, the triethanolamine oleate has a CAS number of 10277-04-0.

[0056] Example 1

[0057] This example provides a preparation method of a fluorine-containing polysiloxane modified with alcohol ammonia for a wire drawing oil applied to the drawing of aluminum-based fine wires, including the following steps:

[0058] A1. Preparation of fluorine-containing polysiloxane

[0059] Weigh: 60 g of D4, 40 g of D3F, 30 g of D4H, and 10 g of 1,1,3,3-tetramethyldisiloxane and add them to a reaction flask and stir for 10 min. Add 3 g of 85 wt% sulfuric acid to the reaction flask. The temperature of the reaction flask is raised to 70 °C, and the reaction is carried out under insulation for 6 h. Then the temperature of the reaction flask is lowered to room temperature. Add a 3 wt% aqueous sodium carbonate solution to the reaction flask to adjust the pH of the system to 6. Let it stand for liquid separation. The upper layer solution is washed twice with saturated sodium carbonate and then washed three times with purified water. The upper layer solution is dried with anhydrous sodium sulfate for 4 h, and then filtered to obtain the fluorine-containing polysiloxane.

[0060] A2. Preparation of epoxidized fluorine-containing polysiloxane

[0061] Weigh: 100 g of fluorine-containing polysiloxane, 2000 mL of isopropanol, and 12 g of 1,2-epoxy-5-hexene and add them to a reaction flask and stir. The temperature of the reaction flask is raised to 76 °C. Add 0.4 g of chloroplatinic acid to the reaction flask. The reaction is carried out under insulation for 5 h, and the temperature of the reaction flask is kept at 76 °C. The low-boiling substances are removed by vacuum distillation to obtain the epoxidized fluorine-containing polysiloxane.

[0062] A3. Preparation of alcohol-amine modified fluorinated polysiloxane

[0063] Weigh: 100 g of epoxidized fluorinated polysiloxane, 200 mL of isopropanol and 20 g of N,N-bis(2-hydroxyethyl)ethylenediamine, add them to a reaction flask and stir. Heat the temperature of the reaction flask to 70 °C, keep the temperature for 4 h, maintain the temperature of the reaction flask at 70 °C, distill off the low-boiling substances under reduced pressure. Lower the temperature of the reaction flask to room temperature, add 300 mL of purified water to the reaction flask, stir and disperse for 20 min, let it stand for liquid separation. Wash the upper layer solution with purified water 3 times, dry the upper layer solution with anhydrous sodium sulfate for 4 h, and filter to obtain alcohol-amine modified fluorinated polysiloxane.

[0064] Example 2

[0065] This example provides a preparation method of alcohol-amine modified fluorinated polysiloxane for wire drawing oil applied to the drawing of aluminum-based fine wires, including the following steps:

[0066] A1. Preparation of fluorinated polysiloxane

[0067] Weigh: 60 g of D4, 40 g of D3F, 30 g of D4H and 10 g of 1,1,3,3-tetramethyldisiloxane, add them to a reaction flask and stir for 13 min. Add 3 g of 90 wt% sulfuric acid to the reaction flask, heat the temperature of the reaction flask to 75 °C, keep the temperature for 7 h, lower the temperature of the reaction flask to room temperature, add 3 wt% sodium carbonate aqueous solution to the reaction flask to adjust the system pH = 6.5, let it stand for liquid separation. Wash the upper layer solution with saturated sodium carbonate 2 times and then with purified water 3 times, dry the upper layer solution with anhydrous sodium sulfate for 4 h, and filter to obtain fluorinated polysiloxane.

[0068] A2. Preparation of epoxidized fluorinated polysiloxane

[0069] Weigh: 100 g of fluorinated polysiloxane, 2000 mL of isopropanol and 12 g of 1,2-epoxy-5-hexene, add them to a reaction flask and stir. Heat the temperature of the reaction flask to 79 °C, add 0.4 g of chloroplatinic acid to the reaction flask, keep the temperature for 5.5 h, maintain the temperature of the reaction flask at 79 °C, distill off the low-boiling substances under reduced pressure to obtain epoxidized fluorinated polysiloxane.

[0070] A3. Preparation of alcohol-amine modified fluorinated polysiloxane

[0071] Weigh: Add 100 g of fluorinated epoxy polysiloxane, 200 mL of isopropanol, and 20 g of N,N-bis(2-hydroxyethyl)ethylenediamine into a reaction flask and stir. Raise the temperature of the reaction flask to 75 °C, keep the temperature for 4.5 h, maintain the temperature of the reaction flask at 75 °C, distill off the low-boiling substances under reduced pressure. Lower the temperature of the reaction flask to room temperature, add 300 mL of purified water to the reaction flask, stir and disperse for 25 min, let it stand for liquid separation. Wash the upper layer solution with purified water 3 times, dry the upper layer solution with anhydrous sodium sulfate for 4 h, and filter to obtain fluorinated polysiloxane modified with alcoholamine.

[0072] Example 3

[0073] This example provides a preparation method of fluorinated polysiloxane modified with alcoholamine for wire drawing oil applied to the drawing of aluminum-based fine wires, including the following steps:

[0074] A1. Preparation of fluorinated polysiloxane

[0075] Weigh: Add 60 g of D4, 40 g of D3F, 30 g of D4H, and 10 g of 1,1,3,3-tetramethyldisiloxane into a reaction flask and stir for 15 min. Add 3 g of 95 wt% sulfuric acid to the reaction flask, raise the temperature of the reaction flask to 80 °C, keep the temperature for 8 h, lower the temperature of the reaction flask to room temperature. Add 3 wt% sodium carbonate aqueous solution to the reaction flask to adjust the system pH = 7, let it stand for liquid separation. Wash the upper layer solution with saturated sodium carbonate 2 times and then with purified water 3 times, dry the upper layer solution with anhydrous sodium sulfate for 4 h, and filter to obtain fluorinated polysiloxane.

[0076] A2. Preparation of fluorinated epoxy polysiloxane

[0077] Weigh: Add 100 g of fluorinated polysiloxane, 2000 mL of isopropanol, and 12 g of 1,2-epoxy-5-hexene into a reaction flask and stir. Raise the temperature of the reaction flask to 82 °C, add 0.4 g of chloroplatinic acid to the reaction flask, keep the temperature for 6 h, maintain the temperature of the reaction flask at 82 °C, distill off the low-boiling substances under reduced pressure to obtain fluorinated epoxy polysiloxane.

[0078] A3. Preparation of fluorinated polysiloxane modified with alcoholamine

[0079] Weigh: Add 100 g of fluorinated epoxy polysiloxane, 200 mL of isopropanol, and 20 g of N,N-bis(2-hydroxyethyl)ethylenediamine into a reaction flask and stir. Raise the temperature of the reaction flask to 80 °C, keep the temperature for 5 h, maintain the temperature of the reaction flask at 80 °C, distill off the low-boiling substances under reduced pressure. Lower the temperature of the reaction flask to room temperature, add 300 mL of purified water to the reaction flask, stir and disperse for 30 min, let it stand for liquid separation. Wash the upper layer solution with purified water 3 times, dry the upper layer solution with anhydrous sodium sulfate for 4 h, and filter to obtain fluorinated polysiloxane modified with alcoholamine.

[0080] Example 4

[0081] This embodiment provides a preparation method of wire-drawing oil applied to the drawing of aluminum-based fine wires, including the following steps:

[0082] S1. Prepare a modifier

[0083] Weigh: 17.5 g of 1-butyl-3-methylimidazolium chloride and 35 mL of absolute ethanol, mix them evenly to obtain a 1-butyl-3-methylimidazolium chloride solution, and set it aside;

[0084] Weigh: 15.4 g of 3,5-dihydroxybenzoic acid, 10.1 g of sodium bicarbonate, and 77 mL of absolute ethanol, add them to a reaction flask and stir until the system dissolves. Raise the temperature of the reaction flask to 40 °C, add the 1-butyl-3-methylimidazolium chloride solution dropwise to the reaction system. After the addition is complete, react at room temperature for 20 h. Lower the temperature of the reaction flask to 5 °C, filter by suction, transfer the filtrate to a rotary evaporator with a water bath temperature of 50 °C, and distill off the low-boiling substances under reduced pressure to obtain an imidazolium salt;

[0085] Add the imidazolium salt and isopropanol to the reaction flask at a ratio of 2 g:3 mL and stir until the system dissolves to obtain an imidazole solution;

[0086] Mix the imidazole solution, triethanolamine borate, and triethanolamine oleate soap evenly according to a weight ratio of 2:5:2 to obtain a modifier.

[0087] S2. Prepare a thickener

[0088] Weigh: 99.2 g of 4,4'-diaminodiphenylmethane, 31.8 g of ethyl 6-aminocaproate, and 496 mL of tetrahydrofuran, add them to a reaction flask protected by argon and stir. Raise the temperature of the reaction flask to 40 °C, add 104.5 g of toluene diisocyanate to the reaction flask, keep the temperature for 60 min, keep the temperature of the reaction flask at 40 °C, and distill off tetrahydrofuran under reduced pressure to obtain a thickener.

[0089] S3. Prepare a modified base oil

[0090] Weigh by weight: 80 parts of neopentyl polyol ester and 15 parts of the modifier in step S1, mix them evenly to obtain a modified base oil.

[0091] S4. Prepare wire-drawing oil.

[0092] Mix dibutylhydroxytoluene, sulfurized fatty acid ester, monoalkenyl succinimide, and dodecanedioic acid evenly according to a weight ratio of 3:2:1:2 to obtain an additive auxiliary agent, and set it aside;

[0093] Weigh by weight: 10 parts of the fluorinated polysiloxane modified by alcohol ammonia prepared in Example 1, 5 parts of the thickener, 3 parts of the additive auxiliary agent, and 95 parts of the modified base oil, mix them evenly to obtain wire-drawing oil.

[0094] Example 5

[0095] This embodiment provides a preparation method of wire drawing oil applied to the drawing of aluminum-based fine wires, including the following steps:

[0096] S1. Prepare a modifier

[0097] Weigh: 17.5 g of 1-butyl-3-methylimidazolium chloride and 35 mL of absolute ethanol, mix them evenly to obtain a 1-butyl-3-methylimidazolium chloride solution, and set it aside;

[0098] Weigh: 15.4 g of 3,5-dihydroxybenzoic acid, 10.1 g of sodium bicarbonate, and 77 mL of absolute ethanol, add them to a reaction flask and stir until the system dissolves. Raise the temperature of the reaction flask to 45 °C, dropwise add the 1-butyl-3-methylimidazolium chloride solution to the reaction system. After the addition is complete, react at room temperature for 22 h. Lower the temperature of the reaction flask to 7 °C, perform suction filtration, transfer the filtrate to a rotary evaporator with a water bath temperature of 55 °C, and distill off the low-boiling substances under reduced pressure to obtain an imidazolium salt;

[0099] Add the imidazolium salt and isopropanol to the reaction flask at a ratio of 2 g:3 mL and stir until the system dissolves to obtain an imidazole solution;

[0100] Mix the imidazole solution, triethanolamine borate, and triethanolamine oleate soap evenly at a weight ratio of 2:5:2 to obtain a modifier.

[0101] S2. Prepare a thickener

[0102] Weigh: 99.2 g of 4,4'-diaminodiphenylmethane, 31.8 g of ethyl 6-aminocaproate, and 496 mL of tetrahydrofuran, add them to a reaction flask under argon protection and stir. Raise the temperature of the reaction flask to 45 °C, add 104.5 g of toluene diisocyanate to the reaction flask, keep the temperature for reaction for 70 min, keep the reaction flask at 45 °C, and distill off tetrahydrofuran under reduced pressure to obtain a thickener.

[0103] S3. Prepare a modified base oil

[0104] Weigh by weight: 85 parts of neopentyl polyol ester and 17 parts of the modifier in step S1, mix them evenly to obtain a modified base oil.

[0105] S4. Prepare wire drawing oil

[0106] Mix dibutylhydroxytoluene, sulfurized fatty acid ester, monoalkenyl succinimide, and dodecanedioic acid evenly at a weight ratio of 3:2:1:2 to obtain an additive auxiliary agent, and set it aside;

[0107] Weigh by weight: 12 parts of the fluorinated polysiloxane modified by alcohol ammonia prepared in Example 2, 6 parts of thickener, 4 parts of additive auxiliary agent, and 102 parts of modified base oil, mix them evenly to obtain wire drawing oil.

[0108] Example 6

[0109] The present example provides a preparation method of wire-drawing oil applied to the drawing of aluminum-based fine wires, including the following steps:

[0110] S1. Prepare a modifier

[0111] Weigh: 17.5 g of 1-butyl-3-methylimidazolium chloride and 35 mL of absolute ethanol, mix them evenly to obtain a 1-butyl-3-methylimidazolium chloride solution, and set it aside;

[0112] Weigh: 15.4 g of 3,5-dihydroxybenzoic acid, 10.1 g of sodium bicarbonate, and 77 mL of absolute ethanol, add them to a reaction flask and stir until the system is dissolved. Raise the temperature of the reaction flask to 50 °C, dropwise add the 1-butyl-3-methylimidazolium chloride solution to the reaction system. After the addition is complete, react at room temperature for 24 h. Lower the temperature of the reaction flask to 10 °C, carry out suction filtration, transfer the filtrate to a rotary evaporator with a water bath temperature of 60 °C, and distill off the low-boiling substances under reduced pressure to obtain an imidazolium ionic salt;

[0113] Add the imidazolium ionic salt and isopropanol to the reaction flask at a ratio of 2 g:3 mL and stir until the system is dissolved to obtain an imidazole solution;

[0114] Mix the imidazole solution, triethanolamine borate, and triethanolamine oleate evenly according to a weight ratio of 2:5:2 to obtain a modifier.

[0115] S2. Prepare a thickener

[0116] Weigh: 99.2 g of 4,4'-diaminodiphenylmethane, 31.8 g of ethyl 6-aminocaproate, and 496 mL of tetrahydrofuran, add them to a reaction flask under argon protection and stir. Raise the temperature of the reaction flask to 50 °C, add 104.5 g of toluene diisocyanate to the reaction flask, keep the reaction at 50 °C for 80 min, and keep the reaction flask at 50 °C, distill off tetrahydrofuran under reduced pressure to obtain a thickener.

[0117] S3. Prepare a modified base oil

[0118] Weigh by weight: 90 parts of neopentyl polyol ester and 20 parts of the modifier in step S1, mix them evenly to obtain a modified base oil.

[0119] S4. Prepare wire-drawing oil

[0120] Mix dibutylhydroxytoluene, sulfurized fatty acid ester, monoalkenyl succinimide, and dodecanedioic acid evenly according to a weight ratio of 3:2:1:2 to obtain an additive auxiliary agent, and set it aside;

[0121] Weigh by weight: 13 parts of the fluorinated polysiloxane modified by alcohol ammonia prepared in Example 3, 7 parts of thickener, 5 parts of additive auxiliary agent, and 110 parts of modified base oil, mix them evenly to obtain wire-drawing oil.

[0122] Comparative Example 1

[0123] The difference between this comparative example and Example 6 is that when preparing the alcohol-amine modified fluorinated polysiloxane, steps A2-A3 are cancelled, and the fluorinated polysiloxane prepared in step A1 is used to replace the alcohol-amine modified fluorinated polysiloxane.

[0124] Comparative Example 2

[0125] The difference between this comparative example and Example 6 is that the imidazole solution is not added to the modifier in step S1.

[0126] Comparative Example 3

[0127] The difference between this comparative example and Example 6 is that ethyl 6-aminocaproate in step S2 is replaced by n-propylamine in equimolar amount.

[0128] Comparative Example 4

[0129] The difference between this comparative example and Example 6 is that neopentyl polyol ester is used as the wire drawing oil.

[0130] Performance test:

[0131] Referring to the standard GB / T 3142-2019 "Determination of the load-carrying capacity of lubricants - Four-ball method", the maximum non-seizure load and wear scar diameter of the wire drawing oil samples prepared in Examples 4-6 and Comparative Examples 1-4 are measured;

[0132] The wire drawing oils prepared in Examples 4-6 and Comparative Examples 1-4 are used in the Changzhou Dingtian DG150-24 double-frequency tension-free rod fine wire drawing machine to draw 0.1 mm aluminum wire, and the wire drawing speed and the breakage rate per 100 tons of the wire drawing operation are statistically analyzed. The specific test results are shown in Table 1 below:

[0133] Table 1 - Performance test data table of the samples

[0134]

[0135] Data analysis:

[0136] By comparing and analyzing the data in Table 1 above, the wire drawing oil prepared by the present invention has a maximum non-seizure load of 768.6 N, the wear scar diameter is reduced to 0.307 mm, the wire drawing speed reaches 2000 m / min, and the breakage rate per 100 tons is reduced to 1.0%. All the performance test data are better than those of the comparative examples. That is, after the base oil is modified by the modifier containing imidazole ionic salt, the alcohol-amine modified fluorinated polysiloxane and the thickener are used to enhance and modify it, which not only effectively increases the extreme pressure and anti-wear performance of the wire drawing oil, but also reduces the breakage rate of drawing 0.1 mm aluminum-based fine wire and improves the production rate of aluminum-based fine wire.

[0137] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, according to the content of this specification, many modifications and variations can be made. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. Wire drawing oil used for aluminum-based fine wire drawing, characterized in that: The invention comprises the following components in parts by weight: 15-20 parts of a modifier, 10-13 parts of an alcohol-amine modified fluorinated polysiloxane, 5-7 parts of a thickener, 3-5 parts of an additive and 80-90 parts of a base oil; The base oil is neopentyl polyol ester; The modifier is composed of imidazole solution, triethanolamine borate and triethanolamine oleate soap in a weight ratio of 2:5:2, and the imidazole solution is composed of imidazolium ion salt and isopropanol in a weight ratio of 2g:3mL; The preparation method of the thickener is as follows: under the protection of an inert atmosphere, 4,4'-diaminodiphenylmethane, blocked ammonia and tetrahydrofuran are stirred and mixed, the temperature of the reaction system is increased to 40-50°C, toluene diisocyanate is added to the reaction system, the reaction is kept warm for 60-80 minutes, and post-processed to obtain the thickener, wherein the blocked ammonia is 6-aminohexanoic acid ethyl ester.

2. The wire drawing oil used for aluminum-based fine wire drawing according to claim 1, characterized in that: The alcohol-amine modified fluorinated polysiloxane is processed by the following steps: A1, stirring and mixing fluorinated polysiloxane, isopropanol and 1,2-epoxy-5-hexene, raising the temperature of the reaction system to 76-82° C., adding a platinum catalyst to the reaction system, keeping the temperature for 5-6 hours, and post-treating to obtain epoxidized fluorinated polysiloxane; A2. The epoxidized fluorinated polysiloxane, isopropanol and N,N-bis(2-hydroxyethyl)ethylenediamine are stirred and mixed, the temperature of the reaction system is raised to 70-80° C., the reaction is kept warm for 4-5 hours, and post-treated to obtain alcohol-amine modified fluorinated polysiloxane.

3. The wire drawing oil for aluminum-based fine wire drawing according to claim 2, characterized in that: In step A1, the amount ratio of the fluorinated polysiloxane, isopropanol, 1,2-epoxy-5-hexene and platinum catalyst is 5g:100mL:0.6g:0.02g, and the platinum catalyst is chloroplatinic acid; in step A2, the amount ratio of the epoxidized fluorinated polysiloxane, isopropanol and N,N-bis(2-hydroxyethyl)ethylenediamine is 5g:10mL:1g.

4. The wire drawing oil for aluminum-based fine wire drawing according to claim 2, characterized in that: The preparation method of fluorinated polysiloxane is as follows: D4, D3F, D4H and 1,1,3,3-tetramethyldisiloxane are stirred and mixed, a catalyst is added to the reaction system, the temperature of the reaction system is increased to 70-80°C, the reaction is kept warm for 6-8h, and post-processed to obtain fluorinated polysiloxane.

5. The wire drawing oil for aluminum-based fine wire drawing according to claim 4, characterized in that: The weight ratio of D4, D3F, D4H, 1,1,3,3-tetramethyldisiloxane and acid catalyst is 6:4:3:1:0.3, and the acid catalyst is 85-95wt% sulfuric acid.

6. The wire drawing oil for aluminum-based fine wire drawing according to claim 1, characterized in that: The usage ratio of the 4,4'-diaminodiphenylmethane, blocked ammonia and toluene diisocyanate is 5 mol:2 mol:6 mol, and the usage ratio of the 4,4'-diaminodiphenylmethane and tetrahydrofuran is 1 g:5 mL.

7. The wire drawing oil for aluminum-based fine wire drawing according to claim 1, characterized in that: The preparation method of the imidazolium ion salt is as follows: 3,5-dihydroxybenzoic acid, sodium bicarbonate and anhydrous ethanol are stirred and mixed until the system is dissolved, the temperature of the reaction system is increased to 40-50° C., 1-butyl-3-methylimidazole chloride solution is added dropwise to the reaction system, and after the addition is completed, the reaction is carried out at room temperature for 20-24 hours, and post-processing is performed to obtain the imidazolium ion salt.

8. The wire drawing oil for aluminum-based fine wire drawing according to claim 7, characterized in that: The dosage ratio of the 3,5-dihydroxybenzoic acid, sodium bicarbonate and 1-butyl-3-methylimidazole chloride is 1 mol:1.2 mol:1 mol, the dosage ratio of the 3,5-dihydroxybenzoic acid and anhydrous ethanol is 1 g:5 mL, and the 1-butyl-3-methylimidazole chloride solution is composed of 1-butyl-3-methylimidazole chloride and anhydrous ethanol at 1 g:2 mL.

9. A method for preparing a wire drawing oil for aluminum-based fine wire drawing according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1, mixing the base oil and the modifier to obtain a modified base oil; S2. Evenly mix the alcohol-ammonia modified fluorinated polysiloxane, thickener, additive and modified base oil to obtain wire drawing oil.

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