Anti-aging oxidation oil-water transmission pipe for automobile and preparation method of anti-aging oxidation oil-water transmission pipe
By preparing anti-aging and oxidation oil-water transmission pipes and using hindered phenolic compounds and polyfluorinated compounds as additives, the aging, oxidation and corrosion problems of oil-water transmission pipes in high temperature and corrosive media environments were solved, achieving performance improvement and life extension.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-13
- Publication Date
- 2026-05-15
AI Technical Summary
Existing automotive oil and water transmission pipes are prone to aging, oxidation, and corrosion in high-temperature and corrosive environments, leading to a decline in performance.
Materials such as nitrile rubber, EPDM rubber, carbon black, nano-alumina, hindered phenolic compounds, polyfluorine compounds, zinc stearate, and paraffin oil are mixed together, and dicumyl peroxide and sulfur are mixed to prepare an anti-aging oxidation oil-water transmission pipe. Hindered phenolic compounds and polyfluorine compounds are used as additives to enhance the antioxidant and corrosion resistance properties.
It significantly improves the anti-aging and oxidation resistance and corrosion resistance of oil-water transmission pipes, extends service life, reduces maintenance costs and replacement frequency, and ensures the long-term stable operation of the oil-water transmission system.
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Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of automotive oil-water transmission systems, specifically to an anti-aging and oxidation-resistant oil-water transmission pipe for automobiles and its preparation method. Background Technology
[0002] Oil and water transmission lines in a car's engine compartment (such as oil lines, transmission oil cooler lines, and turbocharger return lines) are critical components ensuring the normal operation of the powertrain. During long-term use, these lines are constantly exposed to high temperatures and corrosive chemicals, leading to aging, oxidation, and corrosion. This aging, oxidation, and corrosion degrade the performance of the oil and water transmission lines, ultimately affecting the function of the entire oil and water transmission system.
[0003] Therefore, developing an anti-aging and oxidation oil-water transmission pipe for automobiles and its preparation method is of great practical significance. Summary of the Invention
[0004] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide an anti-aging and oxidation oil-water transmission pipe for automobiles and its preparation method, which solves the problem that the existing oil-water transmission pipes have poor anti-aging and oxidation performance and corrosion resistance, which leads to frequent aging, oxidation and corrosion of the oil-water transmission pipes, and thus a decline in the performance of the oil-water transmission pipes.
[0005] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides an anti-aging and oxidation-resistant oil-water transmission pipe for automobiles, comprising the following components by weight: The composition includes 60-70 parts of nitrile rubber, 30-40 parts of ethylene propylene diene monomer (EPDM) rubber, 25-30 parts of carbon black, 8-12 parts of nano-alumina, 1-11 parts of hindered phenolic compounds, 0.8-3.6 parts of polyfluorinated compounds, 1-5 parts of zinc stearate, 3-6 parts of paraffin oil, 2-3 parts of dicumyl peroxide, 0.5-0.9 parts of sulfur, and 1-2 parts of accelerator. The hindered phenolic compound is prepared by the following steps: Step a1: Add 1,3,5-tris(2-hydroxyethyl)cyanuric acid, mercaptopropionic acid, p-toluenesulfonic acid, and toluene to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 20-25℃ and 200-300 r / min for 20-30 min. Then raise the temperature to 120-130℃ and continue stirring for 6-10 h. After the reaction is complete, cool the reaction product to room temperature and pour it into a sodium hydroxide solution. After standing and separating the layers, wash the organic phase 2-3 times with distilled water, dry it with anhydrous sodium sulfate, filter it under vacuum, and remove the solvent by rotary evaporation to obtain the polythiol compound. Step a2: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 2-hydroxyethyl acrylate, and dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 0-5℃ and 200-300 r / min for 30-40 min. Then, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added, and the mixture was stirred for another 10-20 min. The mixture was then heated to 40-50℃ and stirred for another 20-30 h. After the reaction was completed, the product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate, and then purified by silica gel column chromatography with a mixed solvent to obtain an alkenyl hindered phenol compound. Step a3: Add the polythiol compound, the alkenyl hindered phenol compound, benzoin dimethyl ether, and N,N-dimethylacetamide to a beaker. Stir the reaction at 20-25℃, 200-300 r / min, and 20 cm above a 360W UV light source for 5-7 h. After the reaction is complete, remove the solvent by rotary evaporation of the reaction product, then pour it into ethyl acetate. Wash the product 2-3 times with saturated brine and distilled water, then dry it with anhydrous sodium sulfate. Filter the product under vacuum, and remove the solvent by rotary evaporation of the filtrate to obtain the polyhedral phenol compound.
[0006] In a preferred embodiment of the present invention, the ratio of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, mercaptopropionic acid, p-toluenesulfonic acid and toluene in step a1 is 10 mmol: 35-40 mmol: 0.03-0.05 g: 70-80 mL.
[0007] In a preferred embodiment of the present invention, the ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 2-hydroxyethyl acrylate, dichloromethane, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine in step a2 is 10 mmol: 10 mmol: 60-70 mL: 3-4 g: 0.1-0.3 g.
[0008] In a preferred embodiment of the present invention, the mixed solvent in step a2 is a mixture of dichloromethane and methanol in a volume ratio of 20-30:1.
[0009] In a preferred embodiment of the present invention, the ratio of the polythiol compound, the alkenyl hindered phenol compound, benzoin dimethyl ether and N,N-dimethylacetamide in step a3 is 10 mmol: 35-45 mmol: 1-2 g: 80-90 mL.
[0010] In a preferred embodiment of the present invention, the polyfluorinated compound is prepared by the following steps: Tris(4-aminophenyl)amine, perfluorobutylsulfonyl fluoride, triethylamine, and dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 0-5°C and a stirring rate of 200-300 r / min for 2-3 hours. The temperature was then raised to 30-40°C, and the stirring was continued for another 4-5 hours. After the reaction was completed, the product was cooled to room temperature, then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate, and the product was recrystallized with acetone to obtain the polyfluorinated compound.
[0011] In a preferred embodiment of the present invention, the ratio of tris(4-aminophenyl)amine, perfluorobutylsulfonyl fluoride, triethylamine and dichloromethane is 10 mmol: 30 mmol: 40-50 mmol: 80-90 mL.
[0012] Secondly, this application provides a method for preparing an anti-aging and oxidation oil-water transmission pipe for automobiles, comprising the following steps: Step 1: Weigh out 60-70 parts by weight of nitrile rubber, 30-40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 25-30 parts by weight of carbon black, 8-12 parts by weight of nano-alumina, 1-11 parts by weight of hindered phenolic compound, 0.8-3.6 parts by weight of polyfluorine compound, 1-5 parts by weight of zinc stearate, 3-6 parts by weight of paraffin oil, 2-3 parts by weight of dicumyl peroxide, 0.5-0.9 parts by weight of sulfur, and 1-2 parts by weight of accelerator, and set aside. Step 2: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, hindered phenolic compounds, polyfluorine compounds, zinc stearate and paraffin oil to a mixer and mix at 120-140℃ for 8-10 minutes. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 3-5 minutes to obtain the compound. Step 3: Put the compounded rubber into a two-roll mill and pass it through 3-5 times, then crush it to obtain pipe masterbatch; Step 4: Extrude the pipe masterbatch through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0013] In a preferred embodiment of the present invention, the nitrile rubber is N220S.
[0014] In a preferred embodiment of the present invention, the EPDM rubber is EPDM8600.
[0015] In a preferred embodiment of the present invention, the carbon black is N550 carbon black.
[0016] In a preferred embodiment of the present invention, the average particle size of the nano-alumina is 20 nm.
[0017] In a preferred embodiment of the present invention, the accelerator is accelerator CZ.
[0018] The beneficial effects of this invention are: This invention discloses an anti-aging and oxidation-resistant oil-water transmission pipe for automobiles and its preparation method. The method involves mixing nitrile rubber, ethylene propylene diene monomer (EPDM) rubber, carbon black, nano-alumina, hindered phenolic compounds, polyfluorinated compounds, zinc stearate, and paraffin oil in a mixing mill. Then, dicumyl peroxide, sulfur, and an accelerator are added and the mixture is further mixed to obtain a compound. This compound is then passed through a two-roll mill for thin-pass milling and pulverized to obtain a pipe masterbatch. The pipe masterbatch is then extruded through an extruder to obtain the anti-aging and oxidation-resistant oil-water transmission pipe for automobiles. By incorporating hindered phenolic compounds and polyfluorinated compounds as additives, this oil-water transmission pipe significantly enhances its anti-aging and oxidation-resistant properties and oil corrosion resistance. It effectively prevents material aging and corrosion, greatly extending the service life of the oil-water transmission pipe and reducing maintenance costs and replacement frequency caused by aging and corrosion, thereby ensuring the long-term stable operation of the oil-water transmission system.
[0019] In the preparation of the oil-water transmission pipe, a multi-hindered phenolic compound was first prepared. This was achieved through a reaction between 1,3,5-tris(2-hydroxyethyl)cyanuric acid and mercaptopropionic acid, where the hydroxyl group on 1,3,5-tris(2-hydroxyethyl)cyanuric acid reacts with the carboxyl group on mercaptopropionic acid, introducing multiple thiol groups to obtain a multi-thiol compound. This compound was then further prepared through a reaction between 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and 2-hydroxyethyl acrylate, where the carboxyl group on 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid reacts with the hydroxyl group on 2-hydroxyethyl acrylate to form an olefin-containing compound. The product is an alkenyl hindered phenol compound with a hindered phenolic structure. By reacting a polythiol compound with an alkenyl hindered phenolic compound, the thiol group on the polythiol compound undergoes a click chemical reaction with the alkenyl group on the alkenyl hindered phenolic compound to form a multi-hindered phenolic compound containing multiple hindered phenolic structures. The hindered phenolic structures in this multi-hindered phenolic compound have antioxidant capabilities. The antioxidant performance is greatly improved by the synergistic effect of multiple hindered phenolic structures, which can effectively inhibit the oxidation process inside the oil-water transmission pipe, slow down the aging of materials caused by factors such as oxygen and ultraviolet rays, and thus greatly extend the life of the material.
[0020] In the process of preparing the oil-water transmission pipe, a polyfluorinated compound was first prepared. This was achieved through the reaction of tris(4-aminophenyl)amine and perfluorobutylsulfonyl fluoride. The amino group on the tris(4-aminophenyl)amine reacts with the sulfonyl fluoride on the perfluorobutylsulfonyl fluoride, introducing a large number of fluorine atoms to obtain the polyfluorinated compound. This polyfluorinated compound, with its abundant fluorine atoms, can form a dense protective film on the material surface, isolating water, oil, and other corrosive substances from penetration and erosion. This enhances the corrosion resistance of the oil-water transmission pipe, significantly improves its durability, and extends its service life. Detailed Implementation
[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0022] Example 1:
[0023] This embodiment describes a method for preparing an anti-aging and oxidation oil-water transmission pipe for automobiles, comprising the following steps: Step S1: 10 mmol of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 35 mmol of mercaptopropionic acid, 0.03 g of p-toluenesulfonic acid and 70 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 20 °C and 200 r / min for 20 min. Then the temperature was raised to 120 °C and the mixture was stirred for 6 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a sodium hydroxide solution. After standing and separating the layers, the organic phase was washed twice with distilled water and dried with anhydrous sodium sulfate. The mixture was then vacuum filtered and the solvent was removed by rotary evaporation to obtain the polythiol compound. Step S2: 10 mmol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 10 mmol of 2-hydroxyethyl acrylate, and 60 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 0 °C and 200 r / min for 30 min. Then, 3 g of N,N'-dicyclohexylcarbodiimide and 0.1 g of 4-dimethylaminopyridine were added, and the mixture was stirred for another 10 min. The mixture was then heated to 40 °C and stirred for another 20 h. After the reaction was completed, the product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The filtrate was then purified by silica gel column chromatography using a mixed solvent of dichloromethane and methanol in a volume ratio of 20:1 to obtain an alkenyl hindered phenol compound. Step S3: 10 mmol of polythiol compound, 35 mmol of alkenyl hindered phenol compound, 1 g of benzoin dimethyl ether and 80 mL of N,N-dimethylacetamide were added to a beaker and stirred for 5 h at 20 °C, 200 r / min and 20 cm from a 360 W UV light source. After the reaction was completed, the reaction product was removed by rotary evaporation to remove the solvent, and then poured into ethyl acetate. The product was then washed twice with saturated brine and distilled water, and dried with anhydrous sodium sulfate. The product was then filtered under vacuum and the filtrate was removed by rotary evaporation to remove the solvent, yielding the polyhedral phenol compound. Step S4: 10 mmol of tris(4-aminophenyl)amine, 30 mmol of perfluorobutylsulfonyl fluoride, 40 mmol of triethylamine and 80 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 0 °C and 200 r / min for 2 h. Then the temperature was raised to 30 °C and the mixture was stirred for another 4 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The product was then recrystallized with acetone to obtain the polyfluorinated compound. Step S5: Weigh out 60 parts by weight of nitrile rubber, 30 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 25 parts by weight of carbon black, 8 parts by weight of nano-alumina, 1 part by weight of hindered polyphenol compound, 0.8 parts by weight of polyfluorine compound, 1 part by weight of zinc stearate, 3 parts by weight of paraffin oil, 2 parts by weight of dicumyl peroxide, 0.5 parts by weight of sulfur, and 1 part by weight of accelerator, and set aside; the nitrile rubber is N220S; the EPDM rubber is EPDM8600; the carbon black is N550 carbon black; the average particle size of the nano-alumina is 20nm; the accelerator is accelerator CZ; Step S6: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, hindered phenolic compounds, polyfluorine compounds, zinc stearate and paraffin oil to a mixer and mix for 8 minutes at 120°C. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 3 minutes to obtain the compound. Step S7: Put the compounded rubber into a two-roll mill and pass it through three times, then crush it to obtain pipe masterbatch; Step S8: The pipe masterbatch is extruded and molded through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0024] Example 2:
[0025] This embodiment describes a method for preparing an anti-aging and oxidation oil-water transmission pipe for automobiles, comprising the following steps: Step S1: 10 mmol of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 38 mmol of mercaptopropionic acid, 0.04 g of p-toluenesulfonic acid and 75 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 22 °C and 250 r / min for 25 min. Then the temperature was raised to 125 °C and the mixture was stirred for 8 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into sodium hydroxide solution. After standing and separating the layers, the organic phase was washed twice with distilled water and dried with anhydrous sodium sulfate. The mixture was then vacuum filtered and the solvent was removed by rotary evaporation to obtain the polythiol compound. Step S2: 10 mmol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 10 mmol of 2-hydroxyethyl acrylate, and 65 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 3°C and 250 r / min for 35 min. Then, 3.5 g of N,N'-dicyclohexylcarbodiimide and 0.2 g of 4-dimethylaminopyridine were added, and the mixture was stirred for another 15 min. The mixture was then heated to 45°C and stirred for another 25 h. After the reaction was completed, the product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The filtrate was then purified by silica gel column chromatography using a mixed solvent of dichloromethane and methanol in a volume ratio of 25:1 to obtain an alkenyl hindered phenol compound. Step S3: 10 mmol of polythiol compound, 40 mmol of alkenyl hindered phenol compound, 1.5 g of benzoin dimethyl ether and 85 mL of N,N-dimethylacetamide were added to a beaker and stirred for 6 h at a temperature of 22 °C, a stirring rate of 250 r / min and a liquid surface distance of 20 cm from a 360 W UV light source. After the reaction was completed, the reaction product was removed by rotary evaporation to remove the solvent, and then poured into ethyl acetate. The product was then washed twice with saturated brine and distilled water, and dried with anhydrous sodium sulfate. After vacuum filtration, the filtrate was removed by rotary evaporation to remove the solvent, yielding the polyhedral phenol compound. Step S4: 10 mmol of tris(4-aminophenyl)amine, 30 mmol of perfluorobutylsulfonyl fluoride, 45 mmol of triethylamine and 85 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 3°C and 250 r / min for 2.5 h. The temperature was then raised to 35°C and the mixture was stirred for another 4.5 h. After the reaction was completed, the product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The product was then recrystallized with acetone to obtain the polyfluorinated compound. Step S5: Weigh out 65 parts by weight of nitrile rubber, 35 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 28 parts by weight of carbon black, 10 parts by weight of nano-alumina, 6 parts by weight of hindered polyphenol compound, 2.2 parts by weight of polyfluorine compound, 3 parts by weight of zinc stearate, 4.5 parts by weight of paraffin oil, 2.5 parts by weight of dicumyl peroxide, 0.7 parts by weight of sulfur, and 1.5 parts by weight of accelerator, and set aside; the nitrile rubber is N220S; the EPDM rubber is EPDM8600; the carbon black is N550 carbon black; the average particle size of the nano-alumina is 20nm; the accelerator is accelerator CZ; Step S6: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, hindered phenolic compounds, polyfluorine compounds, zinc stearate and paraffin oil to a mixer and mix for 9 minutes at 130°C. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 4 minutes to obtain the compound. Step S7: Put the compounded rubber into a two-roll mill and pass it through four times, then crush it to obtain pipe masterbatch; Step S8: The pipe masterbatch is extruded and molded through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0026] Example 3:
[0027] This embodiment describes a method for preparing an anti-aging and oxidation oil-water transmission pipe for automobiles, comprising the following steps: Step S1: 10 mmol of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 40 mmol of mercaptopropionic acid, 0.05 g of p-toluenesulfonic acid and 80 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 300 r / min for 30 min. Then the temperature was raised to 130 °C and the mixture was stirred for 10 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a sodium hydroxide solution. After standing and separating the layers, the organic phase was washed three times with distilled water and then dried with anhydrous sodium sulfate. The mixture was then vacuum filtered and the solvent was removed by rotary evaporation to obtain the polythiol compound. Step S2: 10 mmol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 10 mmol of 2-hydroxyethyl acrylate, and 70 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 5 °C and 300 r / min for 40 min. Then, 4 g of N,N'-dicyclohexylcarbodiimide and 0.3 g of 4-dimethylaminopyridine were added, and the mixture was stirred for another 20 min. The mixture was then heated to 50 °C and stirred for another 30 h. After the reaction was completed, the product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The product was then purified by silica gel column chromatography using a mixed solvent of dichloromethane and methanol in a volume ratio of 30:1 to obtain an alkenyl hindered phenol compound. Step S3: 10 mmol of polythiol compound, 45 mmol of alkenyl hindered phenol compound, 2 g of benzoin dimethyl ether and 90 mL of N,N-dimethylacetamide were added to a beaker and stirred for 7 h at a temperature of 25 °C, a stirring rate of 300 r / min and a liquid surface distance of 20 cm from a 360 W UV light source. After the reaction was completed, the reaction product was removed by rotary evaporation to remove the solvent, and then poured into ethyl acetate. The product was then washed three times with saturated brine and distilled water, and dried with anhydrous sodium sulfate. The product was then filtered under vacuum and the filtrate was removed by rotary evaporation to remove the solvent, yielding the polyhedral phenol compound. Step S4: 10 mmol of tris(4-aminophenyl)amine, 30 mmol of perfluorobutylsulfonyl fluoride, 50 mmol of triethylamine and 90 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 5 °C and 300 r / min for 3 h. Then the temperature was raised to 40 °C and the mixture was stirred for another 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The product was then recrystallized with acetone to obtain the polyfluorinated compound. Step S5: Weigh out 70 parts by weight of nitrile rubber, 40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 30 parts by weight of carbon black, 12 parts by weight of nano-alumina, 11 parts by weight of hindered polyphenolic compound, 3.6 parts by weight of polyfluorine compound, 5 parts by weight of zinc stearate, 6 parts by weight of paraffin oil, 3 parts by weight of dicumyl peroxide, 0.9 parts by weight of sulfur, and 2 parts by weight of accelerator, and set aside; the nitrile rubber is N220S; the EPDM rubber is EPDM8600; the carbon black is N550 carbon black; the average particle size of the nano-alumina is 20nm; the accelerator is accelerator CZ; Step S6: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, hindered phenolic compounds, polyfluorine compounds, zinc stearate and paraffin oil to a mixer and mix for 10 minutes at 140°C. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 5 minutes to obtain the compound. Step S7: Put the compounded rubber into a two-roll mill and pass it through 5 times, then crush it to obtain pipe masterbatch; Step S8: The pipe masterbatch is extruded and molded through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0028] Comparative Example 1: This comparative example illustrates a method for preparing an anti-aging and oxidation-resistant oil-water transfer pipe for automobiles, comprising the following steps: Step S1: Weigh out 70 parts by weight of nitrile rubber, 40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 30 parts by weight of carbon black, 12 parts by weight of nano-alumina, 5 parts by weight of zinc stearate, 6 parts by weight of paraffin oil, 3 parts by weight of dicumyl peroxide, 0.9 parts by weight of sulfur, and 2 parts by weight of accelerator, and set aside; the nitrile rubber is N220S; the EPDM rubber is EPDM8600; the carbon black is N550 carbon black; the average particle size of the nano-alumina is 20nm; the accelerator is accelerator CZ; Step S2: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, zinc stearate and paraffin oil to a mixer and mix for 10 minutes at 140°C. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 5 minutes to obtain the compound. Step S3: Put the compounded rubber into a two-roll mill and pass it through 5 times, then crush it to obtain pipe masterbatch; Step S4: The pipe masterbatch is extruded and molded through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0029] Comparative Example 2: This comparative example illustrates a method for preparing an anti-aging and oxidation-resistant oil-water transfer pipe for automobiles, comprising the following steps: Step S1: 10 mmol of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 40 mmol of mercaptopropionic acid, 0.05 g of p-toluenesulfonic acid and 80 mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 300 r / min for 30 min. Then the temperature was raised to 130 °C and the mixture was stirred for 10 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a sodium hydroxide solution. After standing and separating the layers, the organic phase was washed three times with distilled water and then dried with anhydrous sodium sulfate. The mixture was then vacuum filtered and the solvent was removed by rotary evaporation to obtain the polythiol compound. Step S2: 10 mmol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 10 mmol of 2-hydroxyethyl acrylate, and 70 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 5 °C and 300 r / min for 40 min. Then, 4 g of N,N'-dicyclohexylcarbodiimide and 0.3 g of 4-dimethylaminopyridine were added, and the mixture was stirred for another 20 min. The mixture was then heated to 50 °C and stirred for another 30 h. After the reaction was completed, the product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The product was then purified by silica gel column chromatography using a mixed solvent of dichloromethane and methanol in a volume ratio of 30:1 to obtain an alkenyl hindered phenol compound. Step S3: 10 mmol of polythiol compound, 45 mmol of alkenyl hindered phenol compound, 2 g of benzoin dimethyl ether and 90 mL of N,N-dimethylacetamide were added to a beaker and stirred for 7 h at a temperature of 25 °C, a stirring rate of 300 r / min and a liquid surface distance of 20 cm from a 360 W UV light source. After the reaction was completed, the reaction product was removed by rotary evaporation to remove the solvent, and then poured into ethyl acetate. The product was then washed three times with saturated brine and distilled water, and dried with anhydrous sodium sulfate. The product was then filtered under vacuum and the filtrate was removed by rotary evaporation to remove the solvent, yielding the polyhedral phenol compound. Step S4: Weigh out 70 parts by weight of nitrile rubber, 40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 30 parts by weight of carbon black, 12 parts by weight of nano-alumina, 11 parts by weight of hindered polyphenol compound, 5 parts by weight of zinc stearate, 6 parts by weight of paraffin oil, 3 parts by weight of dicumyl peroxide, 0.9 parts by weight of sulfur, and 2 parts by weight of accelerator, and set aside; the nitrile rubber is N220S; the EPDM rubber is EPDM8600; the carbon black is N550 carbon black; the average particle size of the nano-alumina is 20nm; the accelerator is accelerator CZ; Step S5: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, hindered phenolic compound, zinc stearate and paraffin oil to a mixer and mix for 10 minutes at 140°C. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 5 minutes to obtain the compound. Step S6: Put the compounded rubber into a two-roll mill and pass it through 5 times, then crush it to obtain pipe masterbatch; Step S7: The pipe masterbatch is extruded and molded through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0030] Comparative Example 3: This comparative example illustrates a method for preparing an anti-aging and oxidation-resistant oil-water transfer pipe for automobiles, comprising the following steps: Step S1: 10 mmol of tris(4-aminophenyl)amine, 30 mmol of perfluorobutylsulfonyl fluoride, 50 mmol of triethylamine and 90 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 5 °C and 300 r / min for 3 h. Then the temperature was raised to 40 °C and the mixture was stirred for another 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then filtered under vacuum. The solvent was removed by rotary evaporation of the filtrate. The product was then recrystallized with acetone to obtain the polyfluorinated compound. Step S2: Weigh out 70 parts by weight of nitrile rubber, 40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 30 parts by weight of carbon black, 12 parts by weight of nano-alumina, 3.6 parts by weight of polyfluorinated compound, 5 parts by weight of zinc stearate, 6 parts by weight of paraffin oil, 3 parts by weight of dicumyl peroxide, 0.9 parts by weight of sulfur, and 2 parts by weight of accelerator, and set aside; the nitrile rubber is N220S; the EPDM rubber is EPDM8600; the carbon black is N550 carbon black; the average particle size of the nano-alumina is 20nm; the accelerator is accelerator CZ; Step S3: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, polyfluorinated compounds, zinc stearate and paraffin oil to a mixer and mix for 10 minutes at 140°C. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 5 minutes to obtain the compound. Step S4: Put the compounded rubber into a two-roll mill and pass it through 5 times, then crush it to obtain pipe masterbatch; Step S5: The pipe masterbatch is extruded and molded through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
[0031] The performance of the automotive anti-aging oxidation oil-water transmission pipes in Examples 1-3 and Comparative Examples 1-3 was tested, and the test results are shown in the table below:
[0032] Referring to the data in the table above, and based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the addition of hindered phenolic compounds and polyfluorinated compounds can significantly improve the anti-aging oxidation performance and oil resistance of oil-water transmission pipes.
[0033] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0034] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.
Claims
1. An anti-aging and oxidation-resistant oil-water transmission pipe for automobiles, characterized in that, Includes the following components by weight: The composition includes 60-70 parts of nitrile rubber, 30-40 parts of ethylene propylene diene monomer (EPDM) rubber, 25-30 parts of carbon black, 8-12 parts of nano-alumina, 1-11 parts of hindered phenolic compounds, 0.8-3.6 parts of polyfluorinated compounds, 1-5 parts of zinc stearate, 3-6 parts of paraffin oil, 2-3 parts of dicumyl peroxide, 0.5-0.9 parts of sulfur, and 1-2 parts of accelerator. The hindered phenolic compound is prepared by the following steps: Step a1: 1,3,5-tris(2-hydroxyethyl)cyanuric acid, mercaptopropionic acid, p-toluenesulfonic acid and toluene were stirred and reacted. After the reaction was completed, the reaction product was cooled and then poured into sodium hydroxide solution. After standing and separating the layers, the organic phase was washed and dried. Then, it was vacuum filtered and the filtrate was evaporated by rotary evaporation to obtain the polythiol compound. Step a2: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 2-hydroxyethyl acrylate and dichloromethane were stirred and reacted. Then N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added and the reaction was continued. After the reaction was completed, the reaction product was cooled and then filtered under vacuum. The filtrate was evaporated by rotary evaporation and then purified by silica gel column chromatography with a mixed solvent to obtain alkenyl hindered phenolic compounds. Step a3: The polythiol compound, the alkenyl hindered phenol compound, benzoin dimethyl ether and N,N-dimethylacetamide were stirred and reacted. After the reaction was completed, the reaction product was evaporated by rotary evaporation and then poured into ethyl acetate. After washing and drying, the product was filtered under vacuum and the filtrate was evaporated by rotary evaporation to obtain the polythiol compound.
2. The automotive anti-aging oxidation oil-water transmission pipe according to claim 1, characterized in that, The ratio of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, mercaptopropionic acid, p-toluenesulfonic acid, and toluene in step a1 is 10 mmol: 35-40 mmol: 0.03-0.05 g: 70-80 mL.
3. The automotive anti-aging oxidation oil-water transmission pipe according to claim 1, characterized in that, The ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 2-hydroxyethyl acrylate, dichloromethane, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine in step a2 is 10 mmol: 10 mmol: 60-70 mL: 3-4 g: 0.1-0.3 g.
4. The automotive anti-aging oxidation oil-water transmission pipe according to claim 1, characterized in that, The mixed solvent in step a2 is a mixture of dichloromethane and methanol in a volume ratio of 20-30:
1.
5. The automotive anti-aging oxidation oil-water transmission pipe according to claim 1, characterized in that, The ratio of the polythiol compound, the alkenyl hindered phenol compound, benzoin dimethyl ether, and N,N-dimethylacetamide used in step a3 is 10 mmol: 35-45 mmol: 1-2 g: 80-90 mL.
6. The automotive anti-aging oxidation oil-water transmission pipe according to claim 1, characterized in that, The polyfluorinated compound was prepared by the following steps: Tris(4-aminophenyl)amine, perfluorobutylsulfonyl fluoride, triethylamine and dichloromethane were stirred and reacted. After the reaction was completed, the reaction product was cooled, then filtered under vacuum, the filtrate was evaporated by rotary evaporation, and then recrystallized to obtain polyfluorinated compounds.
7. The automotive anti-aging oxidation oil-water transmission pipe according to claim 6, characterized in that, The ratio of tris(4-aminophenyl)amine, perfluorobutylsulfonyl fluoride, triethylamine, and dichloromethane is 10 mmol: 30 mmol: 40-50 mmol: 80-90 mL.
8. A method for preparing an anti-aging oxidation oil-water transmission pipe for automobiles as described in any one of claims 1-7, characterized in that, Includes the following steps: Step 1: Weigh out 60-70 parts by weight of nitrile rubber, 30-40 parts by weight of ethylene propylene diene monomer (EPDM) rubber, 25-30 parts by weight of carbon black, 8-12 parts by weight of nano-alumina, 1-11 parts by weight of hindered phenolic compound, 0.8-3.6 parts by weight of polyfluorine compound, 1-5 parts by weight of zinc stearate, 3-6 parts by weight of paraffin oil, 2-3 parts by weight of dicumyl peroxide, 0.5-0.9 parts by weight of sulfur, and 1-2 parts by weight of accelerator, and set aside. Step 2: Add nitrile rubber, EPDM rubber, carbon black, nano alumina, hindered phenolic compounds, polyfluorine compounds, zinc stearate and paraffin oil to a mixer and mix at 120-140℃ for 8-10 minutes. Then add dicumyl peroxide, sulfur and accelerator and continue mixing for 3-5 minutes to obtain the compound. Step 3: Put the compounded rubber into a two-roll mill and pass it through 3-5 times, then crush it to obtain pipe masterbatch; Step 4: Extrude the pipe masterbatch through an extruder to obtain an anti-aging and oxidation oil-water transmission pipe for automobiles.
9. The method for preparing an anti-aging oxidation oil-water transmission pipe for automobiles according to claim 8, characterized in that, The nitrile rubber is N220S; The EPDM rubber is EPDM8600; The carbon black is N550 carbon black; The average particle size of the nano-alumina is 20 nm; The accelerator is accelerator CZ.