An environmentally friendly rust-proof stretching oil and its preparation method

Abstract

The present invention discloses an environment-friendly rust-proof drawing oil and a preparation method thereof, belonging to the technical field of metal processing. Through graft modification of phosphoric acid and boric acid, a modified ricinoleic acid ester as an extreme pressure agent is obtained. By combining the amino group of aminated boron nitride with the carboxyl group of stearic acid, nano boron nitride coated with stearic acid as a nano filler is obtained. Then, through the hydrophobic interaction of β-cyclodextrin, carboxybenzotriazole is included and grafted with triethanolamine to obtain a microcapsule composite organic amine as a rust inhibitor, thereby forming a sulfur / chlorine-free ternary synergistic system, which has good biodegradability and environmental friendliness, has pH-responsive rust prevention, a long rust prevention time and a stable effect, a low friction coefficient, a strong adhesion between the drawing oil and the metal surface, and can prevent the oil film from breaking under extreme pressure, avoiding crack generation, meeting the environmental requirements of the metal processing manufacturing industry.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal processing, and particularly relates to an environmentally friendly rust-proof stretching oil and a preparation method thereof. Background Art

[0002] The metal stretching process is widely used in manufacturing industries such as automobiles and household appliances. Stretching oil is a key auxiliary material to ensure the quality of metal forming. In the prior art, mineral-based stretching oils have problems such as insufficient lubricity leading to large die wear, sulfur / chlorine-containing additives polluting the environment, and cleaning residues causing workpiece corrosion. In recent years, the industry is transforming towards environmental protection and high performance, and there is an urgent need to solve the balance problem of lubricity, environmental protection and cost control. Based on the requirements of the stamping and stretching process, stamping and stretching oils must have excellent lubricity, extreme pressure resistance and rust prevention to avoid problems such as workpiece scratching, sintering, cracking, rusting and insufficient finish caused by factors such as high-temperature friction between the die and the workpiece. The base oils of stamping and stretching oils are mostly narrow-fraction light oils, which more or less contain substances harmful to the environment and human body such as aromatics, olefins and sulfides, and belong to non-environmentally friendly stamping and stretching oils. In the situation of shortage of petrochemical resources and serious environmental pollution, it is of particularly important significance to seek green and environmentally friendly stamping and stretching oils that are inexpensive, easily available, renewable, biodegradable, low-toxic and low-harmful to the human body and the environment, and easy to clean.

[0003] Chinese Patent Publication No. CN102787007B discloses a green and environmentally friendly soluble stamping and stretching oil and a preparation method thereof. The extreme pressure agents used are one or a mixture of two or more of sulfurized fatty acid esters, sulfurized isobutene, sulfurized dipentene, and basic sulfonates. However, relying on sulfur / chlorine-based extreme pressure agents, although they have good lubricity, they are prone to corrode metals and pollute the environment, and cannot meet the requirements of the manufacturing industry for "green processes" and environmental protection. Summary of the Invention

[0004] The purpose of the present invention is to provide an environmentally friendly rust-proof stretching oil and a preparation method thereof. Using hydrogenated esters as the base oil, a sulfur / chlorine-free ternary synergistic system is formed by modified ricinoleic acid ester as the extreme pressure agent, stearic acid-coated nano boron nitride as the nano filler, and microcapsule composite organic amine as the rust inhibitor in the formula, which has good biodegradability and environmental friendliness and meets the environmental protection requirements of the metal processing manufacturing industry.

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

[0006] A preparation method of an environmentally friendly rust-proof stretching oil is prepared by the following steps:

[0007] Step 1: The epoxy-modified castor oil amide is ring-opened under the action of triphenylphosphine, and a phosphoric acid group of dibutyl phosphate nucleophilically substitutes one oxygen atom in the epoxy group to obtain a modified ricinoleic acid ester; carboxybenzotriazole is included by the hydrophobic action of β-cyclodextrin and grafted with triethanolamine to obtain a microcapsule composite organic amine as a rust inhibitor.

[0008] Step 2: Add hydrogenated ester oil to the reaction kettle, stir at 60 - 70 °C and 400 - 500 r / min for 20 - 30 min, then add the modified ricinoleic acid ester and stearic acid-coated nano boron nitride, ultrasonically disperse for 40 - 50 min, continue stirring for 1 - 2 h, then sequentially add the microcapsule composite organic amine, antioxidant, defoamer, and solvent oil, continue stirring for 1 - 2 h, filter, wash the filter cake with deionized water and anhydrous ethanol 2 - 3 times respectively, vacuum dry at 60 - 80 °C for 1 - 2 h, and fill into finished products to obtain an environmentally friendly rust-proof drawing oil.

[0009] Furthermore, the mass ratio of the hydrogenated ester oil, modified ricinoleic acid ester, stearic acid-coated nano boron nitride, microcapsule composite organic amine, antioxidant, defoamer, and solvent oil in Step 2 is 58 - 60:14 - 15:2 - 3:4 - 5:1 - 2:0.4 - 0.5:13 - 14.5.

[0010] Furthermore, the hydrogenated ester oil is any one of hydrogenated diisooctyl adipate, hydrogenated pentaerythritol ester, and hydrogenated palm oil ester.

[0011] Furthermore, the antioxidant is any one of 2,6 - di - tert - butyl - p - cresol, diphenylamine, and alkylated diphenylamine.

[0012] Furthermore, the defoamer is any one of polyacrylate, fatty alcohol, and polydimethylsiloxane.

[0013] Furthermore, the solvent oil is any one or a combination of any ratio of PAO base oil and mineral base oil.

[0014] Furthermore, the modified ricinoleic acid ester in Step 1 is specifically prepared by the following steps:

[0015] Add epoxy-modified castor oil amide and triphenylphosphine to the reaction kettle, stir at 40 - 50 °C and 400 - 500 r / min for 20 - 30 min, then add dibutyl phosphate, heat to 70 - 80 °C, and continue reacting for 3 - 4 h to obtain the modified ricinoleic acid ester.

[0016] Furthermore, the dosage ratio of epoxy-modified castor oil amide, triphenylphosphine, and dibutyl phosphate is 300 - 400 mL:4 - 5 g:300 - 320 mL.

[0017] Furthermore, the epoxy-modified castor oil amide is prepared through the following steps:

[0018] Add the borate-modified castor oil amide and epichlorohydrin into a reaction kettle, stir for 20 - 30 min under the conditions of 20 - 25 °C and 400 - 500 r / min, then add benzyltriethylammonium chloride as a catalyst, heat to 115 - 120 °C, and continue the reaction for 2 - 3 h. After the reaction is completed, cool down to 60 - 70 °C, add calcium oxide and sodium hydroxide, continue the reaction for 3 - 4 h, carry out suction filtration, and rotary evaporation to remove the unreacted epichlorohydrin to obtain the epoxy-modified castor oil amide.

[0019] Furthermore, the dosage ratio of the borate-modified castor oil amide, epichlorohydrin, benzyltriethylammonium chloride, calcium oxide and sodium hydroxide is 300 - 400 mL: 2.4 - 3 L: 3 - 4 mL: 50 - 60 g: 40 - 45 g.

[0020] Furthermore, the borate-modified castor oil amide is prepared through the following steps:

[0021] Add the diethanolamide of castor oil acid, toluene, and p-toluenesulfonic acid as a catalyst into a reaction kettle, stir for 20 - 30 min under the conditions of 140 - 150 °C and 400 - 500 r / min, add the boric acid powder passed through a 100 - 200 mesh sieve into the reaction kettle, evacuate, and continue the reaction for 1.5 - 2 h under the pressure of -0.01 to -0.02 MPa, and naturally cool to room temperature to obtain the borate-modified castor oil amide.

[0022] Furthermore, the dosage ratio of the diethanolamide of castor oil acid, toluene, p-toluenesulfonic acid and boric acid powder is 700 - 800 mL: 120 - 150 mL: 4 - 5 g: 500 - 600 g.

[0023] Furthermore, the diethanolamide of castor oil acid is prepared through the following steps:

[0024] Add the castor oil acid into a reaction kettle, stir for 20 - 30 min under the conditions of 150 - 160 °C and 400 - 500 r / min, then add sodium hydroxide and diethanolamine as catalysts, and continue the reaction for 6 - 7 h. After the reaction is completed, quickly pour out, naturally cool to room temperature, seal and stand still to obtain the diethanolamide of castor oil acid.

[0025] Furthermore, the dosage ratio of the castor oil acid, sodium hydroxide and diethanolamine is 500 - 600 mL: 4 - 5 g: 400 - 450 mL.

[0026] Furthermore, the stearic acid-coated nano boron nitride in step two is prepared through the following steps:

[0027] Add nano boron nitride powder with a particle size of 40 - 50 nm and urea into a ball mill according to a mass ratio of 400 - 500:800 - 900, ball mill for 14 - 15 h under a nitrogen atmosphere and at 0 - 4 °C, wash the product with deionized water 2 - 3 times, and vacuum dry at 60 - 80 °C for 1 - 2 h to obtain amino-functionalized boron nitride; add the amino-functionalized boron nitride, an ethanol solution with a mass fraction of 40 - 50%, and stearic acid into a reaction kettle, stir and dissolve at 45 - 50 °C and 400 - 500 r / min for 20 - 30 min, filter, wash the filter cake with deionized water and absolute ethanol 2 - 3 times respectively, and vacuum dry at 60 - 80 °C for 1 - 2 h to obtain stearic acid-coated nano boron nitride.

[0028] Furthermore, the dosage ratio of the amino-functionalized boron nitride, the ethanol solution, and the stearic acid is 700 - 720 g:1 - 2 L:300 - 400 g.

[0029] Furthermore, the microcapsule composite organic amine in step one is specifically prepared by the following steps:

[0030] Add carboxybenzotriazole, sodium dodecylbenzenesulfonate, and an acetone solution into a reaction kettle, stir at 50 - 60 °C and 400 - 500 r / min for 20 - 30 min, then add a β-cyclodextrin solution with a mass fraction of 14 - 16% and triethanolamine, continue to stir and react for 24 - 26 h, carry out suction filtration, wash the product with deionized water and absolute ethanol 2 - 3 times respectively, and vacuum dry at 60 - 80 °C for 1 - 2 h to obtain the microcapsule composite organic amine.

[0031] Furthermore, the dosage ratio of the carboxybenzotriazole, the sodium dodecylbenzenesulfonate, the acetone solution, the β-cyclodextrin solution, and the triethanolamine is 70 - 80 g:4 - 5 g:800 - 900 mL:200 - 220 mL:50 - 60 mL.

[0032] The beneficial effects of the present invention:

[0033] An environmentally friendly rust-proof drawing oil prepared by the present invention uses hydrogenated esters as the base oil, and forms a ternary synergistic system through the modified ricinoleic acid ester as the extreme pressure agent, the stearic acid-coated nano boron nitride as the nano filler, and the microcapsule composite organic amine as the rust inhibitor in the formula. It has good biodegradability and environmental friendliness, has pH-responsive rust prevention, a long rust prevention time and a stable effect, a low friction coefficient, a strong adhesion between the drawing oil and the metal surface, and can prevent the oil film from breaking and avoid crack generation under extreme pressure.

[0034] The modified ricinoleic acid ester of the present invention contains both phosphorus atoms and boron atoms in its structure. At high friction temperatures, phosphorus reacts with the metal surface to form an inorganic phosphate film. Ammonium borate decomposes at high friction temperatures, releasing active boron atoms that react with the metal surface to form a hard film, significantly reducing the friction coefficient, effectively reducing the friction between the workpiece surface and the mold, and effectively reducing workpiece burns.

[0035] For the stearic acid-coated nano boron nitride of the present invention, the amino group of the aminated boron nitride combines with the carboxyl group of stearic acid to obtain stearic acid-coated nano boron nitride. Stearic acid itself is a long-chain fatty acid that can form a physical adsorption film on the metal surface. At the same time, the layered structure of nano boron nitride provides an ultra-low friction coefficient through interlayer slip. The two work together to further reduce the friction coefficient. During the dynamic friction process, nano boron nitride will be peeled off from the layered structure due to shear force and migrate to the worn area, filling the newly formed microcracks through mechanical interlocking and chemical adsorption, thus ensuring the structural integrity of the workpiece.

[0036] For the microcapsule composite organic amine of the present invention, the hydrophobic cavity of β-cyclodextrin can include carboxybenzotriazole through hydrophobic interaction. The amino group of triethanolamine forms a hydrogen bond network with the outer hydroxyl groups of β-cyclodextrin, increasing the density of the shell layer. As a basic organic amine, triethanolamine can neutralize the acidic corrosion medium on the metal surface. At the same time, its hydroxyl and amino groups form a dense protective film on the metal surface through hydrogen bonding and electrostatic adsorption, blocking the contact of oxygen and moisture. When encountering water, along with the dissolution of β-cyclodextrin, the included carboxybenzotriazole is released. At the same time, triethanolamine releases basic groups, quickly adjusting the local pH value from acidic to alkaline, inhibiting Fe 2+ oxidation and H + corrosion. Carboxybenzotriazole can undergo a coordination reaction with the metal surface to form an insoluble chelate, covering the active sites of the metal and preventing electrochemical corrosion; under acidic conditions, the carboxylic acid group and nitrogen atom of carboxybenzotriazole will be protonated, losing the ability to coordinate with the metal surface, resulting in its inability to form a protective film through chelation. The inclusion effect of β-cyclodextrin can protect carboxybenzotriazole from protonation and maintain its chemical activity. Detailed implementation manners

[0037] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0038] Example 1: A preparation method of an environmentally friendly rust-proof drawing oil is prepared through the following steps:

[0039] S1: Add 500 mL of ricinoleic acid into the reaction kettle, stir for 20 min under the conditions of 150 °C and 400 r / min, then add 4 g of sodium hydroxide as the catalyst and 400 mL of diethanolamine, continue the reaction for 6 h. After the reaction is completed, quickly pour out, cool naturally to room temperature, seal and let stand to obtain diethanolamide ricinoleate.

[0040] There are two active groups in the diethanolamine molecule: amino group and alcohol hydroxyl group, which can respectively carry out amidation or esterification reactions with the carboxyl group of ricinoleic acid, collectively called acylation reaction. At high temperature, the amidation reaction and the esterification reaction proceed simultaneously and belong to competitive reactions with each other. Since the nucleophilicity of the amino group on the diethanolamine molecule is stronger than that of the hydroxyl group, the amidation reaction is the main reaction, and the system mainly exists as diethanolamide ricinoleate at the end of the reaction.

[0041] S2: Add 700 mL of diethanolamide ricinoleate, 120 mL of toluene, and 4 g of p-toluenesulfonic acid as the catalyst into the reaction kettle, stir for 20 min under the conditions of 140 °C and 400 r / min, add 500 g of boric acid powder passed through a 100-mesh sieve into the reaction kettle, evacuate, and continue the reaction for 1.5 h under the pressure of -0.01 MPa, then cool naturally to room temperature to obtain boric acid ester modified castor oil amide.

[0042] There are three hydroxyl groups in the diethanolamine ricinoleate molecule. Due to the relationship between the hydroxyl group activity and steric hindrance, the two hydroxyl groups at the 2nd and 3rd positions can simultaneously carry out esterification reactions with boric acid to obtain boric acid ester modified castor oil amide, and the hydroxyl group at the 1st position is retained.

[0043] S3: Add 300 mL of boric acid ester modified castor oil amide and 2.4 L of epichlorohydrin into the reaction kettle, stir for 20 min under the conditions of 20 °C and 400 r / min, then add 3 mL of benzyltriethylammonium chloride as the catalyst, heat to 115 °C, and continue the reaction for 2 h. After the reaction is completed, cool down to 60 °C, add 50 g of calcium oxide and 40 g of sodium hydroxide, continue the reaction for 3 h, filter by suction, and rotary evaporate to remove the unreacted epichlorohydrin to obtain epoxy modified castor oil amide.

[0044] The hydroxyl group at the 1st position of the boric acid ester modified castor oil amide attacks the epoxy ring of epichlorohydrin and undergoes ring opening under the action of benzyltriethylammonium chloride. After the reaction is completed, the alkaline conditions provided by calcium oxide and sodium hydroxide promote dehydration and ring closure to reform a stable epoxy group.

[0045] S4: Add 300 mL of epoxy modified castor oil amide and 4 g of triphenylphosphine into the reaction kettle, stir for 20 min under the conditions of 40 °C and 400 r / min, then add 300 mL of dibutyl phosphate, heat to 70 °C, and continue the reaction for 3 h to obtain modified castor oil acid ester as the extreme pressure agent.

[0046] Triphenylphosphine acts as a nucleophilic catalyst, attacking the epoxy group in epoxy-modified castor oil amide, opening the epoxy ring to generate an oxygen anion intermediate, enhancing the reaction activity. The phosphate group of dibutyl phosphate attacks the oxygen anion site after ring opening, and a nucleophilic substitution reaction occurs, where the phosphate group replaces one oxygen atom in the epoxy group to form a stable phosphate ester bond.

[0047] S5: Add 400 g of nano boron nitride powder with a particle size of 40 nm and 800 g of urea into a ball mill, ball mill for 14 h under a nitrogen atmosphere and at 0 °C, wash the product twice with deionized water, and dry it in vacuum at 60 °C for 1 h to obtain amino-functionalized boron nitride; add 700 g of amino-functionalized boron nitride, 1 L of ethanol solution with a mass fraction of 40%, and 300 g of stearic acid into a reaction kettle, stir and dissolve at 45 °C and 400 r / min for 20 min, filter, wash the filter cake twice with deionized water and anhydrous ethanol respectively, and dry it in vacuum at 60 °C for 1 h to obtain stearic acid-coated nano boron nitride as a nano filler.

[0048] By combining the amino group of amino-functionalized boron nitride with the carboxyl group of stearic acid, stearic acid-coated nano boron nitride is obtained. Stearic acid itself is a long-chain fatty acid, which can form a physical adsorption film on the metal surface. At the same time, the layered structure of nano boron nitride provides an ultra-low friction coefficient through interlayer slip. The two work together to reduce the friction coefficient. Uncoated nano boron nitride, due to its high surface energy, is prone to forming aggregates, resulting in an abnormal increase in the viscosity of the oil fluid and affecting the lubrication uniformity.

[0049] S6: Add 70 g of carboxybenzotriazole, 4 g of sodium dodecylbenzenesulfonate, and 800 mL of acetone solution into a reaction kettle, stir at 50 °C and 400 r / min for 20 min, then add 200 mL of β-cyclodextrin solution with a mass fraction of 14% and 50 mL of triethanolamine, continue to stir and react for 24 h, filter by suction, wash the product twice with deionized water and anhydrous ethanol respectively, and dry it in vacuum at 60 °C for 1 h to obtain microcapsule composite organic amine as a rust inhibitor.

[0050] The hydrophobic cavity of β-cyclodextrin can include carboxybenzotriazole through hydrophobic interaction. The carboxylic acid group of carboxybenzotriazole forms a hydrogen bond with the hydroxyl group of cyclodextrin to stabilize the inclusion structure. The amino group of triethanolamine forms a hydrogen bond network with the outer hydroxyl groups of β-cyclodextrin, increasing the density of the shell layer. Triethanolamine, as a basic organic amine, can neutralize the acidic corrosion medium on the metal surface. At the same time, its hydroxyl group and amino group form a dense protective film on the metal surface through hydrogen bonding and electrostatic adsorption, blocking the contact of oxygen and moisture. When encountering water, along with the dissolution of β-cyclodextrin, the included carboxybenzotriazole is released. At the same time, triethanolamine releases basic groups, quickly adjusting the local pH from acidic to 8.5 - 9.2 to inhibit Fe 2+ oxidation and H +For corrosion, carboxybenzotriazole can undergo a coordination reaction with the metal surface to form an insoluble chelate, covering the metal active sites and preventing electrochemical corrosion.

[0051] S7: Add 58 g of diisooctyl hydrogen adipate to the reaction kettle, stir for 20 min at 60 °C and 400 r / min, then add 14 g of modified ricinoleic acid ester and 2 g of stearic acid-coated nano boron nitride, ultrasonically disperse for 40 min, continue stirring for 1 h, then successively add 4 g of microcapsule composite organic amine, 1 g of 2,6-di-tert-butyl-p-cresol, 0.4 g of polyacrylate, and 13 g of PAO base oil, continue stirring for 1 h, filter, wash the filter cake twice with deionized water and anhydrous ethanol respectively, dry in vacuum at 60 °C for 1 h, fill into finished products to obtain an environmentally friendly rust-proof drawing oil.

[0052] Example 2: A preparation method of an environmentally friendly rust-proof drawing oil is prepared through the following steps:

[0053] S1: Add 550 mL of ricinoleic acid to the reaction kettle, stir for 25 min at 155 °C and 450 r / min, then add 4.5 g of sodium hydroxide as a catalyst and 425 mL of diethanolamine, continue the reaction for 6.5 h, quickly pour out after the reaction ends, naturally cool to room temperature, seal and stand still to obtain ricinoleic acid diethanolamide.

[0054] S2: Add 750 mL of ricinoleic acid diethanolamide, 135 mL of toluene, and 4.5 g of p-toluenesulfonic acid as a catalyst to the reaction kettle, stir for 25 min at 145 °C and 450 r / min, add 550 g of boric acid powder passed through a 150-mesh sieve to the reaction kettle, evacuate, and continue the reaction for 1.75 h under a pressure of -0.015 MPa, naturally cool to room temperature to obtain boric acid ester-modified ricinoleamide.

[0055] S3: Add 350 mL of boric acid ester-modified ricinoleamide and 2.7 L of epichlorohydrin to the reaction kettle, stir for 25 min at 22.5 °C and 450 r / min, then add 3.5 mL of benzyltriethylammonium chloride as a catalyst, heat to 117.5 °C, continue the reaction for 2.5 h, after the reaction ends, cool to 65 °C, add 55 g of calcium oxide and 42.5 g of sodium hydroxide, continue the reaction for 3.5 h, filter by suction, and rotary evaporate to remove the unreacted epichlorohydrin to obtain epoxy-modified ricinoleamide.

[0056] S4: Add 350 mL of epoxy-modified ricinoleamide and 4.5 g of triphenylphosphine to the reaction kettle, stir for 25 min at 45 °C and 450 r / min, then add 310 mL of dibutyl phosphate, heat to 75 °C, continue the reaction for 3.5 h to obtain a modified ricinoleic acid ester as an extreme pressure agent.

[0057] S5: Add 450 g of nano boron nitride powder with a particle size of 45 nm and 850 g of urea into a ball mill, ball mill for 14.5 h under a nitrogen atmosphere and at 2 °C, wash the product twice with deionized water, and dry it in vacuum at 70 °C for 1.5 h to obtain amino-functionalized boron nitride; Add 710 g of amino-functionalized boron nitride, 1.5 L of ethanol solution with a mass fraction of 45%, and 350 g of stearic acid into a reaction kettle, stir and dissolve for 25 min under the conditions of 47.5 °C and 450 r / min, filter, wash the filter cake twice with deionized water and anhydrous ethanol respectively, and dry it in vacuum at 70 °C for 1.5 h to obtain stearic acid-coated nano boron nitride as a nano filler.

[0058] S6: Add 75 g of carboxybenzotriazole, 4.5 g of sodium dodecylbenzenesulfonate and 850 mL of acetone solution into a reaction kettle, stir for 25 min under the conditions of 55 °C and 450 r / min, then add 210 mL of β-cyclodextrin solution with a mass fraction of 15% and 55 mL of triethanolamine, continue to stir and react for 25 h, carry out suction filtration, wash the product twice with deionized water and anhydrous ethanol respectively, and dry it in vacuum at 70 °C for 1.5 h to obtain microcapsule composite organic amine as a rust inhibitor.

[0059] S7: Add 59 g of hydrogenated pentaerythritol ester into a reaction kettle, stir for 25 min under the conditions of 65 °C and 450 r / min, then add 14.5 g of modified ricinoleic acid ester and 2.5 g of stearic acid-coated nano boron nitride, carry out ultrasonic dispersion for 45 min, continue to stir for 1.5 h, then add 4.5 g of microcapsule composite organic amine, 1.5 g of diphenylamine, 0.45 g of fatty alcohol and 13.75 g of mineral base oil in sequence, continue to stir for 1.5 h, filter, wash the filter cake twice with deionized water and anhydrous ethanol respectively, and dry it in vacuum at 70 °C for 1.5 h, then fill it into finished products to obtain an environmentally friendly rust-proof drawing oil.

[0060] Example 3: A preparation method of an environmentally friendly rust-proof drawing oil is prepared through the following steps:

[0061] S1: Add 600 mL of ricinoleic acid into a reaction kettle, stir for 30 min under the conditions of 160 °C and 500 r / min, then add 5 g of sodium hydroxide as a catalyst and 450 mL of diethanolamine, continue to react for 7 h, quickly pour out after the reaction ends, naturally cool to room temperature, seal and let stand to obtain ricinoleic acid diethanolamide.

[0062] S2: Add 800 mL of diethanolamide ricinoleate, 150 mL of toluene, and 5 g of p-toluenesulfonic acid as a catalyst into the reaction kettle, stir for 30 min under the conditions of 150 °C and 500 r / min, add 600 g of boric acid powder passed through a 200-mesh sieve into the reaction kettle, evacuate, and continue to react for 2 h under a pressure of -0.02 MPa, and then naturally cool to room temperature to obtain boric acid ester-modified ricinoleamide.

[0063] S3: Add 400 mL of boric acid ester-modified ricinoleamide and 3 L of epichlorohydrin into the reaction kettle, stir for 30 min under the conditions of 25 °C and 500 r / min, then add 4 mL of benzyltriethylammonium chloride as a catalyst, heat to 120 °C, and continue to react for 3 h. After the reaction is completed, cool to 70 °C, add 60 g of calcium oxide and 45 g of sodium hydroxide, continue to react for 4 h, filter by suction, and rotary evaporate to remove the unreacted epichlorohydrin to obtain epoxy-modified ricinoleamide.

[0064] S4: Add 400 mL of epoxy-modified ricinoleamide and 5 g of triphenylphosphine into the reaction kettle, stir for 30 min under the conditions of 50 °C and 500 r / min, then add 320 mL of dibutyl phosphate, heat to 80 °C, and continue to react for 4 h to obtain modified ricinoleic acid ester as an extreme pressure agent.

[0065] S5: Add 500 g of nano boron nitride powder with a particle size of 50 nm and 900 g of urea into a ball mill, ball mill for 15 h under a nitrogen atmosphere and at 4 °C, wash the product 3 times with deionized water, and dry in vacuum at 80 °C for 2 h to obtain amino-functionalized boron nitride; add 720 g of amino-functionalized boron nitride, 2 L of ethanol solution with a mass fraction of 50%, and 400 g of stearic acid into the reaction kettle, stir and dissolve for 30 min under the conditions of 50 °C and 500 r / min, filter, wash the filter cake 3 times with deionized water and anhydrous ethanol respectively, and dry in vacuum at 80 °C for 2 h to obtain stearic acid-coated nano boron nitride as a nano filler.

[0066] S6: Add 80 g of carboxybenzotriazole, 5 g of sodium dodecylbenzenesulfonate, and 900 mL of acetone solution into the reaction kettle, stir for 30 min under the conditions of 60 °C and 500 r / min, then add 220 mL of β-cyclodextrin solution with a mass fraction of 16% and 60 mL of triethanolamine, continue to stir and react for 26 h, filter by suction, wash the product 3 times with deionized water and anhydrous ethanol respectively, and dry in vacuum at 80 °C for 2 h to obtain microcapsule composite organic amine as a rust inhibitor.

[0067] S7: Add 60 g of hydrogenated palm oil ester into the reaction kettle, stir for 30 min under the conditions of 70 °C and 500 r / min, then add 15 g of modified ricinoleic acid ester and 3 g of stearic acid-coated nano boron nitride, ultrasonically disperse for 50 min, continue stirring for 2 h, then sequentially add 5 g of microcapsule composite organic amine, 2 g of alkylated diphenylamine, 0.5 g of polydimethylsiloxane, 7.5 g of PAO base oil and 7 g of mineral base oil, continue stirring for 2 h, filter, wash the filter cake 3 times with deionized water and anhydrous ethanol respectively, vacuum dry at 80 °C for 2 h, fill and package the finished product to obtain an environmentally friendly rust-proof drawing oil.

[0068] Comparative Example 1: On the basis of Example 3, replace the modified ricinoleic acid ester in step S7 with commercially available sulfurized fatty acid ester of the same mass, and keep the rest of the steps unchanged to prepare an environmentally friendly rust-proof drawing oil.

[0069] Comparative Example 2: On the basis of Example 3, replace the stearic acid-coated nano boron nitride in step S7 with nano boron nitride powder with a particle size of 50 nm in step S5 of the same mass, and keep the rest of the steps unchanged to prepare an environmentally friendly rust-proof drawing oil.

[0070] Comparative Example 3: On the basis of Example 3, replace the microcapsule composite organic amine in step S7 with commercially available sebacic acid of the same mass, and keep the rest of the steps unchanged to prepare an environmentally friendly rust-proof drawing oil.

[0071] Perform performance tests on the environmentally friendly rust-proof drawing oils obtained in Examples 1 - 3 and Comparative Examples 1 - 3, and the results are shown in Table 1:

[0072] Table 1 Performance test table of environmentally friendly rust-proof drawing oil

[0073] Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Test Method <![CDATA[Kinematic viscosity (40 °C) / mm 2 / s]]> 56 58 60 45 41 49 GB / T 265 Copper Strip Corrosion Degree 1a 1a 1a 2b 1b 2b GB / T 7326-1987 and GB / T 5096-1991 Coefficient of Friction ≤0.06 ≤0.06 ≤0.06 ≤0.16 ≤0.18 ≤0.08 GB / T 3142 PB / N 889 902 932 801 721 870 GB / T 12583-1998

[0074] As can be seen from Table 1, the environmentally friendly rust-proof drawing oil prepared by the present invention does not contain sulfur and chlorine, has good biodegradability and environmental friendliness, has pH-responsive rust prevention, a long rust prevention time and a stable effect, a low friction coefficient, a strong adhesion between the oil product and the metal surface, can prevent the oil film from breaking under extreme pressure, and avoid crack generation.

[0075] In Comparative Example 1, the modified ricinoleic acid ester is replaced with sulfurized fatty acid ester. Sulfurized fatty acid ester contains sulfur, which will produce sulfuric acid or hydrogen sulfide under high-temperature decomposition, accelerate the rusting of steel, and sulfides are volatile and produce pungent odors. Phosphorus atoms and boron atoms. Under high friction temperature, phosphorus will react with the metal surface to form inorganic films such as FePO4 / Cu3(PO4)2. Ammonium borate decomposes under high friction temperature, releases active boron atoms, reacts with the metal surface to form a hard film, significantly reduces the friction coefficient, can effectively reduce the friction between the workpiece surface and the mold, and can effectively reduce workpiece burn.

[0076] In Comparative Example 2, the stearic acid-coated nano boron nitride was replaced with nano boron nitride powder with a particle size of 50 nm in Step S5 of the same mass. The uncoated nano boron nitride, due to its high surface energy, easily forms aggregates, resulting in an abnormal increase in the viscosity of the oil fluid and affecting the lubrication uniformity. During the dynamic friction process, stearic acid will assist the nano boron nitride to migrate to the wear area, fill the newly formed microcracks through mechanical interlocking and chemical adsorption. Under the action of the frictional shear force, the nano boron nitride undergoes directional slip between layers, converting the sliding friction into interlayer internal friction, thereby reducing the friction coefficient.

[0077] In Comparative Example 3, the microcapsule composite organic amine was replaced with commercially available sebacic acid of the same mass. Carboxybenzotriazole is released under the trigger of pH value change or mechanical stress to form a dynamic repair protective film. The hydrophobic cavity of β-cyclodextrin can include the benzene ring structure of carboxybenzotriazole through hydrophobic interaction. The hydroxyl and amino groups of triethanolamine form a hydrogen bond network with the hydroxyl groups on the outer edge of β-cyclodextrin, increasing the density of the shell layer. As a basic organic amine, triethanolamine can neutralize the acidic corrosion medium on the metal surface. At the same time, the amino group of triethanolamine forms a dense protective film on the metal surface through hydrogen bonding and electrostatic adsorption, blocking the contact of oxygen and moisture. When encountering water, along with the dissolution of β-cyclodextrin, the carboxybenzotriazole contained therein is released. At the same time, triethanolamine releases basic groups, quickly adjusting the local pH value from acidic to 8.5 - 9.2 to inhibit Fe 2+ oxidation and H + corrosion. Carboxybenzotriazole can undergo a coordination reaction with the metal surface to generate an insoluble chelate, covering the active sites of the metal and preventing electrochemical corrosion.

[0078] It should be noted that in this article, terms such as "including", "comprising" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or elements inherent to such a process, method, article or device.

[0079] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention.

Claims

1. A preparation method of an environmentally friendly rust-proof stretching oil, characterized in that, It includes the following steps: Step 1: The epoxy-modified castor oil amide is ring-opened under the action of triphenylphosphine, and one oxygen atom in the epoxy group is nucleophilically substituted by the phosphate group of dibutyl phosphate to obtain a modified castor oil acid ester; the carboxybenzotriazole is included by the hydrophobic action of β-cyclodextrin and grafted with triethanolamine to obtain a microcapsule composite organic amine as a rust inhibitor; Step 2: Add hydrogenated ester oil to the reaction kettle, stir at 60 - 70 °C and 400 - 500 r / min for 20 - 30 min, then add the modified castor oil acid ester and stearic acid-coated nano boron nitride, ultrasonically disperse for 40 - 50 min, continue to stir for 1 - 2 h, then successively add the microcapsule composite organic amine, antioxidant, defoamer and solvent oil, continue to stir for 1 - 2 h, filter, wash, vacuum dry, fill and package the finished product to obtain an environmentally friendly rust-proof stretching oil.

2. The preparation method of an environmentally friendly rust-proof stretching oil according to claim 1, characterized in that, In Step 2, the mass ratio of the hydrogenated ester oil, modified castor oil acid ester, stearic acid-coated nano boron nitride, microcapsule composite organic amine, antioxidant, defoamer and solvent oil is 58 - 60:14 - 15:2 - 3:4 - 5:1 - 2:0.4 - 0.5:13 - 14.

5.

3. The preparation method of an environmentally friendly rust-proof stretching oil according to claim 1, characterized in that, The hydrogenated ester oil in Step 2 is any one of hydrogenated diisooctyl adipate, hydrogenated pentaerythritol ester, and hydrogenated palm oil ester; the antioxidant is any one of 2,6-di-tert-butyl-p-cresol, diphenylamine, and alkylated diphenylamine; the defoamer is any one of polyacrylate, fatty alcohol, and polydimethylsiloxane; the solvent oil is any one or a combination of any ratio of PAO base oil and mineral base oil.

4. The preparation method of an environmentally friendly rust-proof stretching oil according to claim 1, characterized in that The modified castor oil acid ester in Step 1 is specifically prepared by the following steps: Add epoxy-modified castor oil amide and triphenylphosphine to the reaction kettle, stir at 40 - 50 °C and 400 - 500 r / min for 20 - 30 min, then add dibutyl phosphate, heat to 70 - 80 °C, and continue to react for 3 - 4 h to obtain the modified castor oil acid ester; The dosage ratio of the epoxy-modified castor oil amide, triphenylphosphine, and dibutyl phosphate is 300 - 400 mL:4 - 5 g:300 - 320 mL.

5. The preparation method of an environmentally friendly rust-proof stretching oil according to claim 4, characterized in that, The epoxy-modified castor oil amide is prepared by the following steps: Add borate-modified castor oil amide and epichlorohydrin to the reaction kettle, stir at 20 - 25 °C and 400 - 500 r / min for 20 - 30 min, then add benzyltriethylammonium chloride, heat to 115 - 120 °C, and continue to react for 2 - 3 h. After the reaction is completed, cool to 60 - 70 °C, add calcium oxide and sodium hydroxide, and continue to react for 3 - 4 h. Filter by suction, and rotary evaporate to remove the unreacted epichlorohydrin to obtain the epoxy-modified castor oil amide; The dosage ratio of the borate-modified castor oil amide, epichlorohydrin, benzyltriethylammonium chloride, calcium oxide, and sodium hydroxide is 300 - 400 mL:2.4 - 3 L:3 - 4 mL:50 - 60 g:40 - 45 g.

6. The preparation method of an environmentally friendly rust-proof stretching oil according to claim 5, characterized in that, The borate-modified castor oil amide is prepared by the following steps: Add ricinoleic acid diethanolamide, toluene, and p-toluenesulfonic acid into a reaction kettle, stir at 140 - 150 °C and 400 - 500 r / min for 20 - 30 min, add boric acid powder passed through a 100 - 200 mesh sieve into the reaction kettle, evacuate the air, and continue to react under a pressure of -0.01 to -0.02 MPa for 1.5 - 2 h, then naturally cool to room temperature to obtain boric acid ester modified castor oil amide; The dosage ratio of the ricinoleic acid diethanolamide, toluene, p-toluenesulfonic acid, and boric acid powder is 700 - 800 mL : 120 - 150 mL : 4 - 5 g : 500 - 600 g.

7. The preparation method of an environmentally friendly rust-proof drawing oil according to claim 6, characterized in that, The ricinoleic acid diethanolamide is prepared through the following steps: Add ricinoleic acid into a reaction kettle, stir at 150 - 160 °C and 400 - 500 r / min for 20 - 30 min, then add sodium hydroxide and diethanolamine, and continue to react for 6 - 7 h. After the reaction ends, quickly pour out, naturally cool to room temperature, seal and let stand to obtain ricinoleic acid diethanolamide; The dosage ratio of the ricinoleic acid, sodium hydroxide, and diethanolamine is 500 - 600 mL : 4 - 5 g : 400 - 450 mL.

8. The preparation method of an environmentally friendly rust-proof drawing oil according to claim 1, characterized in that, The stearic acid-coated nano boron nitride in step two is prepared through the following steps: Add nano boron nitride powder with a particle size of 40 - 50 nm and urea into a ball mill according to a mass ratio of 400 - 500 : 800 - 900, ball mill under a nitrogen atmosphere and at 0 - 4 °C for 14 - 15 h, wash, and vacuum dry to obtain amino-functionalized boron nitride; Add the amino-functionalized boron nitride, 40 - 50 wt% ethanol solution, and stearic acid into a reaction kettle, stir and dissolve at 45 - 50 °C and 400 - 500 r / min for 20 - 30 min, filter, wash, and vacuum dry to obtain stearic acid-coated nano boron nitride; The dosage ratio of the amino-functionalized boron nitride, ethanol solution, and stearic acid is 700 - 720 g : 1 - 2 L : 300 - 400 g.

9. The preparation method of an environmentally friendly rust-proof stretching oil according to claim 1, characterized in that, The microcapsule composite organic amine in step one is specifically prepared through the following steps: Add carboxybenzotriazole, sodium dodecylbenzenesulfonate, and acetone solution into a reaction kettle, stir at 50 - 60 °C and 400 - 500 r / min for 20 - 30 min, then add 14 - 16 wt% β-cyclodextrin solution and triethanolamine, and continue to stir and react for 24 - 26 h, filter by suction, wash, and vacuum dry to obtain microcapsule composite organic amine; The dosage ratio of the carboxybenzotriazole, sodium dodecylbenzenesulfonate, acetone solution, β-cyclodextrin solution, and triethanolamine is 70 - 80 g : 4 - 5 g : 800 - 900 mL : 200 - 220 mL : 50 - 60 mL.

10. An environmentally friendly rust-proof stretching oil, characterized in that, Prepared by the preparation method described in any one of claims 1 - 9.