CN114317068B - Lubricating oil for automobile engine and preparation method and application thereof - Google Patents
Lubricating oil for automobile engine and preparation method and application thereof Download PDFInfo
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- CN114317068B CN114317068B CN202111582136.4A CN202111582136A CN114317068B CN 114317068 B CN114317068 B CN 114317068B CN 202111582136 A CN202111582136 A CN 202111582136A CN 114317068 B CN114317068 B CN 114317068B
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 84
- 239000002105 nanoparticle Substances 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 46
- ZVVWZNFSMIFGEP-UHFFFAOYSA-N 2-(4-ethoxyphenyl)acetic acid Chemical compound CCOC1=CC=C(CC(O)=O)C=C1 ZVVWZNFSMIFGEP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005751 Copper oxide Substances 0.000 claims abstract description 20
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 20
- 239000002199 base oil Substances 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 230000000994 depressogenic effect Effects 0.000 claims abstract description 16
- -1 2, 5-dimercaptothiadiazole zinc salt Chemical compound 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000001050 lubricating effect Effects 0.000 claims abstract description 9
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 44
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- QTVUDNOFBZLOHM-UHFFFAOYSA-N n-(2-methylpropyl)propanamide Chemical compound CCC(=O)NCC(C)C QTVUDNOFBZLOHM-UHFFFAOYSA-N 0.000 claims description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007821 HATU Substances 0.000 claims description 10
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000010705 motor oil Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920000193 polymethacrylate Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
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- 238000004140 cleaning Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 1
- SWRLHCAIEJHDDS-UHFFFAOYSA-N [Mn].[Cu].[Zn] Chemical compound [Mn].[Cu].[Zn] SWRLHCAIEJHDDS-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/62—Hybrid vehicles
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Abstract
The application discloses lubricating oil for an automobile engine, a preparation method and application thereof, belongs to the technical field of new energy hybrid automobile engine lubricating oil, and comprises the following raw materials in parts by weight: 80-85 parts of base oil, 0.5-2 parts of composite nano particles, 1-5 parts of a first antiwear agent, 1-20 parts of a second antiwear agent, 0.5-3 parts of an extreme pressure agent, 6-10 parts of a viscosity index improver, 0.2-0.4 part of a pour point depressant, 0.5-1 part of an antioxidant and 0.1-1 part of an anti-foaming agent; the extreme pressure agent comprises 2, 5-dimercaptothiadiazole zinc salt and vanadyl naphthenate; the composite nano-particles are prepared from 4-ethoxyphenylacetic acid, nano-copper oxide and nano-copper sulfide. The lubricating oil can meet the lubricating requirement of intermittent operation of the engine in a short-time low-temperature state, reduce the fretting wear of the engine, is suitable for the traditional fuel vehicle in a low-temperature area, can also be matched with the hybrid vehicle type, particularly the plug-in hybrid engine working condition, ensures the normal output of the performance of the hybrid vehicle type engine, and prolongs the service life of the engine.
Description
Technical Field
The application relates to lubricating oil for an automobile engine, a preparation method and application thereof, and belongs to the technical field of new energy hybrid automobile engine lubricating oil.
Background
Lubricating oil is a fluid medium which is widely used in mechanical devices and mainly plays a role in lubrication. The engine is the heart of an automobile, a plurality of metal surfaces which mutually rub and move are arranged in the engine, and in order to ensure the continuous and reliable running of the engine, different types of engines should select engine oil with matched performance. Lubricating oils generally comprise two parts, a base oil, which determines the basic properties of the oil, and additives, which improve the overall properties of the oil or impart new properties to the oil.
Along with the rapid development of new energy automobiles, a plurality of hybrid automobiles such as oil-electric hybrid, light hybrid, plug-in hybrid, extended range and the like appear, meanwhile, not only the traditional fuel automobile has special requirements on engine lubricating oil, but also the hybrid automobiles, especially the plug-in hybrid automobiles, have short engine running time, lower running temperature and higher starting and stopping frequency because the hybrid automobiles need to be continuously switched between fuel driving and electric driving, which means that the automobile type has higher requirements on engine oil viscosity, wear resistance, low-temperature fluidity and the like in the aspect of engine oil selection compared with the traditional gasoline/diesel engine automobile type; in addition, if the conventional engine lubricating oil is used for a hybrid vehicle, oil sludge is easily formed on the wall of the engine cavity along with partial water vapor due to frequent change of the temperature of the engine oil, and the performance of the engine is affected.
Chinese patent CN 111500342A-a special lubricating oil for automobile engines and a preparation method thereof disclose a lubricating oil added with nano materials, but nano substances are easy to lose, the wear resistance of the lubricating oil is still to be improved, and the low-temperature fluidity is limited, so that the lubricating requirement of hybrid series automobile types is difficult to meet.
Disclosure of Invention
In order to solve the problems, the lubricating oil for the automobile engine and the preparation method and application thereof are provided, the composite nanoparticles, the first anti-wear agent, the second anti-wear agent and the extreme pressure agent are used, the composite nanoparticles are better in dispersity, the lubricating oil is low in viscosity and excellent in anti-wear performance in a low-temperature state and has good cleaning capacity, the lubricating requirement of the engine for discontinuous operation in a short-time low-temperature state can be met, the fretting wear of the engine is reduced, the lubricating oil is suitable for a traditional fuel vehicle in a low-temperature area and can be matched with a hybrid vehicle type, particularly with the working condition of a plug-in hybrid engine, an excellent lubricating effect is achieved, the normal output of the performance of the hybrid vehicle type engine is ensured, and the service life of the hybrid vehicle type engine is prolonged.
According to one aspect of the application, the lubricating oil for the automobile engine is prepared from the following raw materials in parts by weight: 80-85 parts of base oil, 0.5-2 parts of composite nano particles, 1-5 parts of a first antiwear agent, 1-20 parts of a second antiwear agent, 0.5-3 parts of an extreme pressure agent, 6-10 parts of a viscosity index improver, 0.2-0.4 part of a pour point depressant, 0.5-1 part of an antioxidant and 0.1-1 part of an anti-foaming agent;
the extreme pressure agent comprises 2, 5-dimercaptothiadiazole zinc salt and vanadyl naphthenate; the composite nano-particles are prepared from 4-ethoxyphenylacetic acid, nano-copper oxide and nano-copper sulfide.
Optionally, the weight ratio of 4-ethoxyphenylacetic acid, nano copper oxide and nano copper sulfide in the composite nano particle is (2-10): (1-5): (0.5-2): (0.4-0.8).
Optionally, the method for preparing the composite nanoparticle comprises the following steps: adding 4-ethoxy phenylacetic acid into ethanol, stirring, adding nanometer copper, nanometer copper oxide and nanometer copper sulfide, stirring and heating at 60-80 deg.C for 2-3 hr, centrifuging for 1-1.5 hr, and ultrasonic drying.
Preferably, the preparation method of the composite nanoparticle comprises the following steps: adding 4-ethoxyphenyl acetic acid into ethanol, wherein the amount of the ethanol is 5 times of that of the 4-ethoxyphenyl acetic acid, the stirring speed is 120r/min, then adding nano copper, nano copper oxide and nano copper sulfide, stirring and heating for 2h at 70 ℃, centrifuging for 1h at 3000rpm, performing ultrasonic treatment and drying at 50 ℃ to obtain the copper-zinc-manganese composite material.
Optionally, the first antiwear agent is prepared by synthesizing 2-vinylbenzoic acid and N-isobutylpropionamide. Preferably, the weight ratio of the 2-vinylbenzoic acid to the N-isobutylpropionamide is 1 (0.7-0.9).
Optionally, the preparation method of the first antiwear agent comprises the following steps: adding a condensing agent into 2-vinylbenzoic acid, uniformly stirring, adding N-isobutylpropionamide, stirring for 12-15h, washing and drying to obtain the compound;
the condensing agent is HATU (2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyluronium hexafluorophosphate) or HBTU (O-benzotriazol-tetramethyluronium hexafluorophosphate). Preferably, the condensing agent is HATU in an amount of 1.5 times that of 2-vinylbenzoic acid.
Preferably, the preparation method of the first antiwear agent comprises the following steps: adding HATU into 2-vinylbenzoic acid, stirring for 1h, adding N-isobutylpropionamide, stirring for 13h at 30 ℃, washing with deionized water for three times, and drying to obtain the product.
Optionally, the structural formula of the first antiwear agent is shown as formula 1
Optionally, the weight ratio of the 2, 5-dimercaptothiadiazole zinc salt to the vanadyl naphthenate in the extreme pressure agent is 1: (0.5-2).
Optionally, the viscosity index improver is poly hydrogenated styrene isoprene, the pour point depressant is polymethacrylate, the antioxidant is 2, 6-di-tert-butyl alpha-dimethylamino-p-cresol, the anti-foaming agent is methyl silicone oil, and the second anti-grinding agent is molybdenum dialkyl dithiophosphate.
According to another aspect of the present application, there is provided a method for preparing the above lubricating oil, comprising the steps of:
(1) mixing the viscosity index improver, the pour point depressant and the antioxidant, uniformly stirring, then adding the second anti-grinding agent and the anti-foaming agent, heating to 50-60 ℃, and stirring for 1-2 hours to obtain a mixture;
(2) adding an extreme pressure agent and composite nano particles into base oil, adding the mixture obtained in the step (1), uniformly stirring, adding a first antiwear agent, keeping the temperature at 45-55 ℃, stirring for 5-6h, and ultrasonically dispersing for 40-50min to obtain the lubricating oil.
According to yet another aspect of the present application, there is provided a use of the above-mentioned lubricating oil, which is suitable for providing lubrication as an engine lubricating oil for pure fuel, hybrid electric, light hybrid, plug-in hybrid and extended range vehicles.
Benefits of the present application include, but are not limited to:
1. according to the lubricating oil for the automobile engine, by using the composite nano particles, the first anti-wear agent, the second anti-wear agent and the extreme pressure agent, the composite nano particles are better in dispersity, the lubricating oil is low in viscosity and excellent in wear resistance in a low-temperature state, and the lubricating oil further has good cleaning capacity, can meet the lubricating requirement of the engine for intermittent operation in a short time and in a low-temperature state, reduces the fretting wear of the engine, is suitable for the traditional fuel oil vehicle in a low-temperature area, can be matched with the type of a hybrid vehicle, particularly the working condition of an inserted hybrid vehicle, plays an excellent lubricating effect, ensures the normal output of the performance of the hybrid vehicle type engine, and prolongs the service life of the hybrid vehicle type engine.
2. According to the lubricating oil for the automobile engine, the pits on the wear surface of the inner wall of the engine can be filled with the composite nano particles, and the protective film is formed on the surface of the inner wall of the engine after the composite nano particles are rubbed with the base oil, so that the composite nano particles roll on the surface of the film to change the original sliding friction into the combination of the rolling friction and the sliding friction, the friction coefficient of the inner wall is reduced, and the wear resistance is enhanced.
3. According to the lubricating oil for the automobile engine, the nano copper oxide and the nano copper sulfide are coated by using the 4-ethoxyphenyl acetic acid and then prepared into the nano particles, so that on one hand, the dispersion uniformity of nano substances can be improved, and the phenomenon that the nano substances are added independently to cause agglomeration and cannot form an effective protective film is avoided; on the other hand, 4-ethoxy phenyl acetic acid is used as a carrier, so that the compression stress concentration generated by high pressure when an engine runs can be borne by more nano particles, and the burning loss caused by independently adding nano substances can be obviously reduced; in addition, the nano copper oxide and the nano copper sulfide can enhance the bearing area of the prepared composite nano particles, reduce the contact stress and further improve the wear resistance.
4. According to the lubricating oil for the automobile engine, the weight ratio of the nano substances in the composite nano particles is limited, so that the dispersion uniformity of the substances in the 4-ethoxyphenyl acetic acid can be improved, and the prepared composite nano particles can be stably deposited on the pit surfaces of the inner wall of the engine.
5. According to the lubricating oil for the automobile engine, 2-vinylbenzoic acid, N-isobutyl propionamide and a condensing agent are used for reacting, carboxyl in the 2-vinylbenzoic acid and secondary amine in the N-isobutyl propionamide are condensed to form an amide group, and a second anti-grinding agent is finally obtained, wherein the second anti-grinding agent can form a layer of organic surface film on the basis of a protective film formed by composite nano particles, so that the integral film structure has certain toughness, the strength of the integral film is improved, the adhesion of the composite nano particles can be improved, the composite nano particles can play a role of a micro bearing, the failure load of base oil is improved, the friction resistance is reduced, and the wear resistance is improved; in addition, the organic matter surface film can adsorb oxidation products and oil sludge, and has a good cleaning effect.
6. According to the lubricating oil for the automobile engine, by using the second anti-wear agent and the extreme pressure agent, the molybdenum dialkyl dithiophosphate can enhance the anti-wear performance, and the 2, 5-dimercaptothiadiazole zinc salt can generate a substance with a low melting point with metal at a high temperature, so that the fretting wear of the engine is reduced, and certain oil-saving and noise-reducing effects are achieved; vanadyl naphthenate can react with metal friction pairs, so that the microstructure of metal is improved, the friction pairs are strengthened, the bearing capacity of the friction pairs is improved, the friction coefficient is reduced, the non-seizing load is improved, the diameter of a wear scar is reduced, and a certain viscosity reduction capacity is used, so that an excellent lubricating effect is achieved.
7. The preparation method of the lubricating oil for the automobile engine is simple in preparation process and suitable for industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic view of a graph of a wear reduction test according to example 4 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, reagents such as raw materials in examples of the present application are commercially available, and parameters and methods not mentioned are those used in the prior art.
The base oil used in this application was fully synthetic base oil (PAO) produced by ExxonMobil Chemical (ExxonMobil).
EXAMPLE 1 preparation of lubricating oil No. 1
The lubricating oil 1# is prepared from the following raw materials in parts by weight: 82 parts of base oil, 1 part of composite nano-particles, 3 parts of a first antiwear agent, 10 parts of a second antiwear agent, 2 parts of an extreme pressure agent, 8 parts of a viscosity index improver, 0.3 part of a pour point depressant, 0.8 part of an antioxidant and 0.5 part of an anti-foaming agent;
the extreme pressure agent comprises 2, 5-dimercaptothiadiazole zinc salt and vanadyl naphthenate in a weight ratio of 1: 1; the composite nano-particles are prepared from 4-ethoxyphenylacetic acid, nano-copper oxide and nano-copper sulfide, wherein the weight ratio is 5: 2: 1: 0.6; the preparation method comprises the following steps: adding 4-ethoxyphenyl acetic acid into ethanol, wherein the amount of the ethanol is 5 times of that of the 4-ethoxyphenyl acetic acid, the stirring speed is 120r/min, then adding nano copper, nano copper oxide and nano copper sulfide, stirring and heating for 2h at 70 ℃, centrifuging for 1h at 3000rpm, performing ultrasonic treatment, and drying at 50 ℃ to obtain the product.
The first antiwear agent is prepared by synthesizing 2-vinyl benzoic acid and N-isobutyl propionamide, wherein the weight ratio of the 2-vinyl benzoic acid to the N-isobutyl propionamide is 1:0.8, and the preparation method comprises the following steps: adding HATU into 2-vinylbenzoic acid, wherein the dosage of HATU is 1.5 times of that of 2-vinylbenzoic acid, stirring for 1h, adding N-isobutylpropionamide, stirring for 13h at 30 ℃, washing for three times by using deionized water, and drying to obtain the product.
The viscosity index improver is poly hydrogenated styrene isoprene, the pour point depressant is polymethacrylate, the antioxidant is 2, 6-di-tert-butyl alpha-dimethylamino-p-cresol, the anti-foaming agent is methyl silicone oil, and the second anti-wear agent is molybdenum dialkyl dithiophosphate.
The preparation method of the lubricating oil 1# comprises the following steps:
(1) mixing the viscosity index improver, the pour point depressant and the antioxidant, uniformly stirring, then adding the second anti-wear agent and the anti-foaming agent, heating to 55 ℃, and stirring for 1.5 hours to obtain a mixture;
(2) adding an extreme pressure agent and composite nano particles into base oil, adding the mixture obtained in the step (1), uniformly stirring, adding a first antiwear agent, keeping the temperature at 50 ℃, stirring for 5.5 hours, and ultrasonically dispersing for 45min to obtain the lubricating oil 1 #.
EXAMPLE 2 preparation of lubricating oil # 2
The lubricating oil No. 2 is prepared from the following raw materials in parts by weight: 80 parts of base oil, 0.5 part of composite nano-particles, 1 part of first antiwear agent, 5 parts of second antiwear agent, 0.5 part of extreme pressure agent, 6 parts of viscosity index improver, 0.2 part of pour point depressant, 0.5 part of antioxidant and 0.1 part of anti-foaming agent;
the extreme pressure agent comprises 2, 5-dimercaptothiadiazole zinc salt and vanadyl naphthenate in a weight ratio of 1: 0.5; the composite nano-particles are prepared from 4-ethoxyphenylacetic acid, nano-copper oxide and nano-copper sulfide in a weight ratio of 2: 1: 0.5: 0.4; the preparation method comprises the following steps: adding 4-ethoxyphenyl acetic acid into ethanol, wherein the amount of the ethanol is 5 times of that of the 4-ethoxyphenyl acetic acid, the stirring speed is 120r/min, then adding nano copper, nano copper oxide and nano copper sulfide, stirring and heating for 2h at 60 ℃, centrifuging for 1h at 3000rpm, performing ultrasonic treatment, and drying at 50 ℃ to obtain the product.
The first antiwear agent is prepared by synthesizing 2-vinyl benzoic acid and N-isobutyl propionamide, wherein the weight ratio of the 2-vinyl benzoic acid to the N-isobutyl propionamide is 1:0.7, and the preparation method comprises the following steps: adding HATU into 2-vinylbenzoic acid, wherein the dosage of HATU is 1.5 times of that of 2-vinylbenzoic acid, stirring for 1h, adding N-isobutylpropionamide, stirring for 12h at 30 ℃, washing for three times by using deionized water, and drying to obtain the product.
The viscosity index improver is poly hydrogenated styrene isoprene, the pour point depressant is polymethacrylate, the antioxidant is 2, 6-di-tert-butyl alpha-dimethylamino-p-cresol, the anti-foaming agent is methyl silicone oil, and the second anti-grinding agent is dialkyl molybdenum dithiophosphate.
The preparation method of the lubricating oil No. 2 comprises the following steps:
(1) mixing the viscosity index improver, the pour point depressant and the antioxidant, uniformly stirring, then adding the second anti-grinding agent and the anti-foaming agent, heating to 50 ℃, and stirring for 1h to obtain a mixture;
(2) adding an extreme pressure agent and composite nano particles into base oil, adding the mixture obtained in the step (1), uniformly stirring, adding a first antiwear agent, keeping the temperature at 45 ℃, stirring for 5 hours, and performing ultrasonic dispersion for 40 minutes to obtain lubricating oil No. 2.
EXAMPLE 3 preparation of lubricating oil # 3
The lubricating oil No. 3 is prepared from the following raw materials in parts by weight: 85 parts of base oil, 5 parts of composite nano particles, 5 parts of a first antiwear agent, 20 parts of a second antiwear agent, 3 parts of an extreme pressure agent, 10 parts of a viscosity index improver, 0.4 part of a pour point depressant, 1 part of an antioxidant and 1 part of an antifoaming agent;
the extreme pressure agent comprises 2, 5-dimercaptothiadiazole zinc salt and vanadyl naphthenate in a weight ratio of 1: 2; the composite nano-particles are prepared from 4-ethoxyphenylacetic acid, nano-copper oxide and nano-copper sulfide, and the weight ratio is 10: 5: 2: 0.8; the preparation method comprises the following steps: adding 4-ethoxyphenyl acetic acid into ethanol, wherein the amount of the ethanol is 5 times of that of the 4-ethoxyphenyl acetic acid, the stirring speed is 120r/min, then adding nano copper, nano copper oxide and nano copper sulfide, stirring and heating for 3 hours at 80 ℃, centrifuging for 1.5 hours at 3000rpm, performing ultrasonic treatment and drying at 50 ℃ to obtain the copper-doped zinc sulfide.
The first antiwear agent is prepared by synthesizing 2-vinyl benzoic acid and N-isobutyl propionamide, wherein the weight ratio of the 2-vinyl benzoic acid to the N-isobutyl propionamide is 1:0.9, and the preparation method comprises the following steps: adding HATU into 2-vinylbenzoic acid, wherein the dosage of HATU is 1.5 times of that of 2-vinylbenzoic acid, stirring for 1h, adding N-isobutylpropionamide, stirring for 15h at 30 ℃, washing for three times by using deionized water, and drying to obtain the product.
The viscosity index improver is poly hydrogenated styrene isoprene, the pour point depressant is polymethacrylate, the antioxidant is 2, 6-di-tert-butyl alpha-dimethylamino-p-cresol, the anti-foaming agent is methyl silicone oil, and the second anti-wear agent is molybdenum dialkyl dithiophosphate.
The preparation method of the lubricating oil No. 3 comprises the following steps:
(1) mixing the viscosity index improver, the pour point depressant and the antioxidant, uniformly stirring, then adding the second anti-grinding agent and the anti-foaming agent, heating to 60 ℃, and stirring for 2 hours to obtain a mixture;
(2) adding the extreme pressure agent and the composite nano particles into base oil, adding the mixture obtained in the step (1), uniformly stirring, adding the first antiwear agent, keeping the temperature at 55 ℃, stirring for 6 hours, and ultrasonically dispersing for 50 minutes to obtain the lubricating oil No. 3.
Comparative example 1 preparation of lubricating oil No. 4
Lubricating oil # 4 was prepared in the same manner as lubricating oil # 1, except that: lubricating oil No. 4 used no extreme pressure agent, and the remainder was the same.
Comparative example 2 preparation of lubricating oil No. 5
Lubricating oil # 5 was prepared in the same manner as lubricating oil # 1, except that: lubricating oil No. 5 used only 2, 5-dimercaptothiadiazole zinc salt as an extreme pressure agent, and the rest were the same.
Comparative example 3 preparation of lubricating oil No. 6
Lubricating oil 6# was prepared in the same manner as lubricating oil 1# except that: the lubricating oil No. 6 does not use composite nano particles, and uses nano copper powder and nano copper oxide to replace the composite nano particles, wherein the weight ratio of the nano copper powder to the nano copper oxide is 1:1, and the rest is the same.
Comparative example 4 preparation of lubricating oil No. 7
Lubricating oil 7# was prepared the same as lubricating oil 1# except that: the composition of the composite nano-particles in lubricating oil No. 7 does not use nano-copper sulfide, and the rest is the same.
Comparative example 5 preparation of lubricating oil No. 8
Lubricating oil No. 8 was prepared in the same manner as lubricating oil No. 1 except that: the first antiwear agent was not used in lubricating oil No. 8, and the rest was the same.
Comparative example 6 preparation of lubricating oil No. 9
Lubricating oil # 9 was prepared in the same manner as lubricating oil # 1, except that: the part of the first antiwear agent in lubricating oil No. 9 is 10 parts, and the rest parts are the same.
Example 4 Performance testing
1. Stability test
The experimental method comprises the following steps: (1) respectively taking equal amount of lubricating oil No. 1-9, vacuum sealing at 25 deg.C, naturally standing for 100 days, and observing its settlement;
(2) taking equal amount of lubricating oil No. 1-9, centrifuging for 3h under 100r/min after 400W ultrasonic dispersion, and observing the sedimentation condition.
The results of the above experiments are shown in table 1.
TABLE 1 stability test results
The results in table 1 show that the lubricating oil 1# -3# prepared by using the raw materials, the parts and the method defined in the application has no sedimentation after natural placement and centrifugation for 3h in 100 days, which indicates that the stability is excellent and the dispersion effect of the composite nano particles in the lubricating oil is good; lubricating oil No. 4 does not use an extreme pressure agent, and lubricating oil No. 5 uses a single component as the extreme pressure agent and finally has little or trace sedimentation; the lubricating oil No. 6 uses only nanometer components (nanometer copper and nanometer copper oxide) which are added separately in the prior art, finally, the lubricating oil is naturally placed for 100 days to generate a large amount of settlement, more settlement occurs after centrifugation, and the analysis reason is mainly that the nanometer components are not uniformly dispersed and the agglomeration phenomenon occurs; the formula of the composite nano particles in the lubricating oil 7# is different from that of the lubricating oil 1#, trace settlement occurs after the composite nano particles are naturally placed finally, and a small amount of settlement occurs after the composite nano particles are centrifuged; the first antiwear agent is not used in the lubricating oil No. 8, a large amount of sedimentation occurs after natural placement for 100 days finally, more sedimentation occurs after centrifugation, and the analysis reason is mainly that the dispersibility among the composite nano particles is poor; the first antiwear agent used in lubricating oil # 9 was in excess and eventually allowed to settle to a slight extent after natural standing and centrifugation.
2. Abrasion resistance
Respectively taking lubricating oil 1# -9# as samples, carrying out a four-ball experiment according to GB/T3142-2019, carrying out an experiment according to SH/T0189, and respectively testing P B (maximum No seizure load), P D (sintering load) and the diameter of the wear scar, the results are shown in Table 2.
TABLE 2 abrasion resistance test results
From the results in Table 2, it can be seen that lubricating oils 1# -3#, P were prepared using the raw materials, parts and methods defined in this application B And P D The lubricating oil is obviously higher than other lubricating oil, and the wear-resisting spot diameter is small and is in the range of 0.3-0.35, which shows that the lubricating oil No. 1-3 has high oil film strength and excellent extreme pressure anti-wear performance, and can meet the high requirement of a hybrid vehicle type on the anti-wear performance of the lubricating oil; lubricating oil No. 4 used no extreme pressure agent, and lubricating oil No. 5 used a single component as extreme pressure agent final P B And P D The extreme pressure wear resistance is poor as shown by the fact that the extreme pressure wear resistance is not high and the wear-resisting spot diameter is large; the lubricating oil No. 6 uses the nano-components (nano-copper and nano-copper oxide) which are only added independently in the prior art, and the results show that the wear resistance is poor, and the reason for analyzing the wear resistance is mainly that the loss of the single nano-components is high and the dispersibility is poor; the formula of the composite nano particles in the lubricating oil 7# is different from that of the lubricating oil 1#, and the final result shows that the wear resistance of the lubricating oil is general; the lubricating oil No. 8 does not use a first antiwear agent, and the final result shows that the antiwear performance of the lubricating oil is poor, and the reason for the analysis is mainly that the dispersibility of the composite nano particles is poor, and the strength of a single oil film is low; the first antiwear agent used in lubricating oil # 9 was in excess, with the end result showing a modest antiwear performance.
3. Attrition reduction test
Lubricating oils 1# -3# were respectively used, and a four-ball wear test was performed by using a friction wear tester of MMW21 type and a method of ASTM D41724, to obtain curves of the three types of lubricating oils in which the friction coefficients change with the increase of test load, and the results are shown in fig. 1.
As can be seen from FIG. 1, the lubricating oils 1# -3# prepared by the raw materials, parts and methods defined in the present application all have lower friction coefficients, and compared with the base oil, the friction coefficient can be reduced by about 31% on average, and the requirement of a hybrid vehicle type on low abrasion of the lubricating oil can be met.
4. Viscosity measurement
The kinematic viscosities of the different lubricants at 40 ℃ and 100 ℃ were measured using an IPND401 kinematic viscosity tester with the same amounts of lubricants 1# -9# respectively, and the results are shown in Table 3.
Table 3 results of viscosity measurements
From the results in table 3, it can be seen that the lubricating oil 1# -3# prepared by using the raw materials, parts and method defined in the present application has low viscosity at low temperature and good low temperature fluidity, and can meet the lubricating requirement of the hybrid vehicle during cold start, and the viscosity at high temperature can also match the requirement of the engine; the 4# to 9# lubricating oil has higher viscosity and poorer low-temperature fluidity, has limited lubrication during cold start of a hybrid vehicle type, and can still meet the lubrication requirement of a fuel vehicle type.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. The lubricating oil for the automobile engine is characterized by being prepared from the following raw materials in parts by weight: 80-85 parts of base oil, 0.5-2 parts of composite nano particles, 1-5 parts of a first antiwear agent, 1-20 parts of a second antiwear agent, 0.5-3 parts of an extreme pressure agent, 6-10 parts of a viscosity index improver, 0.2-0.4 part of a pour point depressant, 0.5-1 part of an antioxidant and 0.1-1 part of an anti-foaming agent;
the extreme pressure agent consists of 2, 5-dimercaptothiadiazole zinc salt and vanadyl naphthenate, wherein the weight ratio of the 2, 5-dimercaptothiadiazole zinc salt to the vanadyl naphthenate in the extreme pressure agent is 1: (0.5-2); the composite nano-particles are prepared from 4-ethoxyphenylacetic acid, nano-copper oxide and nano-copper sulfide;
the structural formula of the first antiwear agent is shown as formula 1
the second antiwear agent is molybdenum dialkyl dithiophosphate; the weight ratio of 4-ethoxy phenylacetic acid, nano copper oxide and nano copper sulfide in the composite nano particles is (2-10): (1-5): (0.5-2): (0.4-0.8); the preparation method of the composite nano-particles comprises the following steps: adding 4-ethoxyphenylacetic acid into ethanol, stirring, adding nano copper, nano copper oxide and nano copper sulfide, stirring and heating at 60-80 deg.C for 2-3 hr, centrifuging for 1-1.5 hr, and ultrasonic drying.
2. The lubricating oil of claim 1, wherein the first antiwear agent is prepared synthetically from 2-vinylbenzoic acid and N-isobutylpropionamide.
3. The lubricating oil of claim 2, wherein the first antiwear agent is prepared by a method comprising the steps of: adding a condensing agent into 2-vinylbenzoic acid, uniformly stirring, adding N-isobutylpropionamide, stirring for 12-15h, washing and drying to obtain the compound;
the condensing agent is HATU or HBTU.
4. The lubricating oil of claim 1, wherein the viscosity index improver is polyhydrostyrene isoprene, the pour point depressant is polymethacrylate, the antioxidant is 2, 6-di-tert-butyl alpha-dimethylamino-p-cresol, and the anti-foaming agent is methyl silicone oil.
5. A process for the preparation of the lubricating oil according to any one of claims 1 to 4, comprising the steps of:
(1) mixing the viscosity index improver, the pour point depressant and the antioxidant, uniformly stirring, then adding the second anti-grinding agent and the anti-foaming agent, heating to 50-60 ℃, and stirring for 1-2 hours to obtain a mixture;
(2) adding an extreme pressure agent and composite nano particles into base oil, adding the mixture obtained in the step (1), uniformly stirring, adding a first antiwear agent, keeping the temperature at 45-55 ℃, stirring for 5-6h, and ultrasonically dispersing for 40-50min to obtain the lubricating oil.
6. Use of the lubricating oil according to any one of claims 1 to 4 or prepared by the preparation method according to claim 5, for lubricating an engine oil for a pure fuel, oil-electric hybrid, light hybrid, plug-in hybrid and extended-range vehicle.
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