CN117586823B - Ashless antiwear hydraulic oil and preparation method thereof - Google Patents
Ashless antiwear hydraulic oil and preparation method thereof Download PDFInfo
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- CN117586823B CN117586823B CN202311717179.8A CN202311717179A CN117586823B CN 117586823 B CN117586823 B CN 117586823B CN 202311717179 A CN202311717179 A CN 202311717179A CN 117586823 B CN117586823 B CN 117586823B
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- base oil
- hydraulic oil
- oil
- antiwear hydraulic
- ashless antiwear
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- 239000010720 hydraulic oil Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002199 base oil Substances 0.000 claims abstract description 80
- 239000000654 additive Substances 0.000 claims abstract description 31
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 27
- 239000008139 complexing agent Substances 0.000 claims abstract description 26
- 230000000994 depressogenic effect Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- -1 aryl phosphate Chemical compound 0.000 claims description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229920013639 polyalphaolefin Polymers 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical class CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001565 benzotriazoles Chemical class 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- QQVGEJLUEOSDBB-KTKRTIGZSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CO)(CO)CO QQVGEJLUEOSDBB-KTKRTIGZSA-N 0.000 claims description 3
- 239000013556 antirust agent Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- ZOYYLYJJZVGFJC-UHFFFAOYSA-N o-dihydroxyphosphinothioylhydroxylamine Chemical compound NOP(O)(O)=S ZOYYLYJJZVGFJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 150000004867 thiadiazoles Chemical class 0.000 claims description 3
- IVTHSFJXIARUFL-UHFFFAOYSA-N triazanium;thiophosphate Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=S IVTHSFJXIARUFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 3
- 238000000034 method Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 25
- 239000001263 FEMA 3042 Substances 0.000 description 25
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 25
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 25
- 229940033123 tannic acid Drugs 0.000 description 25
- 235000015523 tannic acid Nutrition 0.000 description 25
- 229920002258 tannic acid Polymers 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910000881 Cu alloy Chemical group 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/14—Metal deactivation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/24—Emulsion properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention relates to the field of lubricating oil processing, in particular to ashless antiwear hydraulic oil and a preparation method thereof; the composition of the additive comprises 98-99% of base oil, 0.7-1.6% of ashless antiwear hydraulic oil complexing agent and 0.3-0.5% of base oil additive by mass percent, wherein the base oil additive comprises pour point depressant and liquid metal nano droplets. The ashless antiwear hydraulic oil disclosed by the invention has the advantages that all components are cooperated, so that the hydraulic oil has excellent viscosity-temperature performance, low-temperature performance, oxidation resistance and shear stability, has the capability of being used in high-pressure, low-temperature and other severe environments, has good extreme pressure performance and thermal oxidation stability, has good antiwear performance, has a performance far higher than the technical index required by the national standard, and has long service life and wide application range.
Description
Technical Field
The invention relates to the field of lubricating oil processing, in particular to ashless antiwear hydraulic oil and a preparation method thereof.
Background
Antiwear hydraulic oil, also called HM hydraulic oil, originates from rust-proof and antioxidant hydraulic oil, which is prepared by adding carefully chosen auxiliary agents into mineral oil. The antiwear hydraulic oil is a hydraulic medium used by a hydraulic system utilizing hydraulic pressure energy, plays roles in energy transmission, system lubrication, corrosion prevention, rust prevention, cooling and the like in the hydraulic system, and is widely used in an automobile brake system, a hoisting system, a bulldozer system, an airplane, a ship and the like.
Currently, antiwear hydraulic oils can also be largely classified into zinc type antiwear hydraulic oils (gray type) and ashless type antiwear hydraulic oils, depending on the additive composition. The antiwear agent in zinc-based antiwear hydraulic oil is mainly zinc dialkyl dithiophosphate, and zinc-based antiwear hydraulic oil can easily pass through a vane pump, but is more difficult to pass through a plunger pump, because ZDDP in the formula causes serious corrosion to copper plating parts of a high-pressure plunger in use, so that the hydraulic pump is damaged, and when a small amount of water is mixed in the oil, serious emulsification occurs, so that a filtering system is blocked.
The zinc-free antiwear hydraulic oil is a branch of hydraulic oil, and can be prepared by adopting S, P type of ash-free extreme pressure antiwear agent, and has a plurality of performances which are not possessed by zinc-containing antiwear hydraulic oil.
The prior ashless type antiwear hydraulic oil does not react with silver-bearing parts because of no zinc and other metal salts in use, thus the ashless type antiwear hydraulic oil does not corrode copper parts, and is more suitable for plunger pumps with copper or copper alloy parts. However, the extreme pressure antiwear performance is not as good as that of zinc type antiwear hydraulic oil, and is one of important indexes for measuring the quality of hydraulic oil, which is crucial for normal operation of high-pressure vane pump and other equipment, and clearly limits the application of ashless type antiwear hydraulic oil. Therefore, how to provide an ashless hydraulic oil with excellent extreme pressure performance, thermal oxidation stability and wear resistance for use in high-pressure and low-temperature environments is a problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide ashless antiwear hydraulic oil, in particular:
The ashless antiwear hydraulic oil comprises the following components in percentage by mass: 98-99% of base oil, 0.7-1.6% of ashless antiwear hydraulic oil complexing agent and 0.3-0.5% of base oil additive;
wherein the base oil is a mixture of a CTL base oil and a metallocene polyalphaolefin base oil;
The ashless antiwear hydraulic oil complexing agent comprises 9-14% of base oil, 50-60% of extreme pressure antiwear agent, 5-8% of antirust agent, 10-20% of antioxidant, 2-4% of metal passivating agent and 0.1-0.8% of emulsifying agent;
The basic oil additive comprises a pour point depressant and liquid metal nano-droplets.
Preferably, the mass ratio of the CTL base oil to the metallocene poly-alpha-olefin base oil in the base oil is 4.8-6.2:1.
Preferably, the mass ratio of the CTL base oil to the metallocene poly-alpha-olefin base oil in the base oil is 5.5-6.2:1.
Preferably, in the base oil additive, the mass ratio of the pour point depressant to the liquid metal nano-droplets is 1.2-1.4:1.
Preferably, in the base oil additive, the pour point depressant is3-301、1-248.
Preferably, the liquid metal nano-droplet is DDP@GLM.
DDP@GLM is a DDP functionalized gallium-based liquid metal nano-droplet. The preparation method comprises the following steps: fully mixing an equivalent tannic acid TA solution with the concentration of 10mg/ml and a Tannic Acid (TA) -Fe 3+ complex solution with the concentration of 10mg/mlFeCl 3·6H2 O at normal temperature to form a Tannic Acid (TA) -Fe 3+ complex solution for standby; 300mg of gallium-based liquid metal is sucked by a syringe and injected into a sample bottle, then 10ml of Tannic Acid (TA) -Fe 3+ complex solution is added, a cell breaker is used for processing for 4 hours at normal temperature and normal pressure to form a suspension, finally 12.1mg of 2-amino-2- (hydroxymethyl) -1, 3-propanediol is added into the obtained suspension to adjust the pH value to 8-9, and then 10ml of dialkyl dithiophosphate DDP is added for stirring, so that DDP functionalized liquid metal GLM nano droplets are formed.
Preferably, in the ashless antiwear hydraulic oil complexing agent, the extreme pressure antiwear agent may be one or more of triphenyl thiophosphate, tricresyl phosphate, ammonium thiophosphate, aryl phosphate and amino thiophosphate.
Preferably, in the ashless antiwear hydraulic oil complexing agent, the antioxidant can be one or more of N-phenyl-alpha-aniline, alkyl diphenylamine, 2, 6-di-tert-butyl-p-cresol and hindered phenol; the rust inhibitor can be one or more of olefine butyl diacid, oleic acid glycol ester, pentaerythritol monooleate and 1,2, 3-trimethyl benzotriazole; the metal passivating agent can be one or more of benzotriazole derivatives, thiadiazole derivatives and methylbenzotriazole derivatives; the anti-emulsifying agent can be one or more of glycol ester and polyether polymers; the base oil is at least one of Zhonghai oil 150N and Mobil 150N.
The preparation method of the ashless antiwear hydraulic oil complexing agent comprises the following steps: the raw materials with the above proportions are put into a reaction kettle, stirred and heated to 50-60 ℃, and the temperature is kept at 60-70 ℃ for continuous stirring and mixing for 4-6 hours, thus obtaining the ashless antiwear hydraulic oil complexing agent.
The second purpose of the invention is to provide a preparation method of ashless antiwear hydraulic oil, in particular:
the preparation method of the ashless antiwear hydraulic oil comprises the following preparation steps:
Adding 98-99% of base oil by mass into a reaction kettle, stirring, heating to 50-60 ℃ while heating, adding 0.7-1.6% of ashless antiwear hydraulic oil complexing agent by mass and 0.3-0.5% of base oil additive by mass, and keeping stirring at 55-65 ℃ for 5-6 hours until uniformly mixed, thus obtaining the ashless antiwear hydraulic oil.
The invention has the beneficial effects that: the ashless antiwear hydraulic oil disclosed by the invention has the advantages that all components are cooperated, so that the hydraulic oil has excellent viscosity-temperature performance, low-temperature performance, oxidation resistance and shear stability, has the capability of being used in high-pressure, low-temperature and other severe environments, has good extreme pressure performance and thermal oxidation stability, has good antiwear performance, has a performance far higher than the technical index required by the national standard, and has long service life and wide application range.
The preparation method of the ashless antiwear hydraulic oil is simple, the raw materials and the equipment used are simple and easy to obtain, and the implementation is convenient.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
The ashless antiwear hydraulic oil comprises the following components in percentage by mass: 98-99% of base oil, 0.7-1.6% of ashless antiwear hydraulic oil complexing agent and 0.3-0.5% of base oil additive;
Wherein the base oil adopts CTL base oil and metallocene poly alpha olefin base oil according to the mass ratio of 4.8-6.2:1, mixing to form;
in some specific embodiments, the mass ratio of CTL base oil to metallocene polyalphaolefin base oil is preferably from 5.5 to 6.2:1, further optimizing the viscosity-temperature performance and the low-temperature fluidity of the hydraulic oil.
In some specific embodiments, the ashless antiwear hydraulic oil complexing agent comprises 9-14% of base oil, 50-60% of extreme pressure antiwear agent, 5-8% of rust inhibitor, 10-20% of antioxidant, 2-4% of metal deactivator and 0.1-0.8% of antichemical agent;
Further, the extreme pressure antiwear agent can be one or more of triphenyl thiophosphate, tricresyl phosphate, ammonium thiophosphate, aryl phosphate and amino thiophosphate. The antioxidant can be one or more of N-phenyl-alpha-aniline, alkyl diphenylamine, 2, 6-di-tert-butyl-p-cresol and hindered phenol. The rust inhibitor can be one or more of olefine butyl diacid, oleic acid glycol ester, pentaerythritol monooleate and 1,2, 3-trimethyl benzotriazole. The metal passivating agent can be one or more of benzotriazole derivatives, thiadiazole derivatives and methylbenzotriazole derivatives. The anticoasis agent can be one or more of glycol ester and polyether polymer. The base oil is at least one of Zhonghai oil 150N and Mobil 150N.
The preparation method of the ashless antiwear hydraulic oil complexing agent comprises the following steps: and (3) weighing the components according to the proportion for standby, putting the components into a reaction kettle, stirring and heating to 50-60 ℃, keeping the temperature at 60-70 ℃ and continuously stirring and mixing for 4-6 hours to obtain the ashless antiwear hydraulic oil complexing agent.
In some specific embodiments, the base oil additive includes a pour point depressant and liquid metal nanodroplets.
Further, the mass ratio of the pour point depressant to the liquid metal nano-droplets is 1.2-1.4:1. and pour point depressant can be selected3-301、/>1-248.
Further, the liquid metal nano-droplet is DDP@GLM. DDP@GLM is a DDP (dialkyl dithiophosphate) -functionalized gallium-based liquid metal nanodrop.
Further, the gallium-based liquid metal may use any one of gallium indium alloy, gallium tin alloy, and gallium indium tin alloy.
The preparation method comprises the following steps: fully mixing an equivalent tannic acid TA solution with the concentration of 10mg/ml and a Tannic Acid (TA) -Fe 3+ complex solution with the concentration of 10mg/mlFeCl 3·6H2 O at normal temperature to form a Tannic Acid (TA) -Fe 3+ complex solution for standby; and (3) sucking 300mg of gallium-based liquid metal by using a syringe, injecting the liquid metal into a sample bottle, adding 10ml of Tannic Acid (TA) -Fe 3+ complex solution, treating the solution for 4 hours at normal temperature and normal pressure by using a cell disruption instrument to form a suspension, finally adding 2-amino-2- (hydroxymethyl) -1, 3-propanediol into the obtained suspension to adjust the pH value to 8-9, and adding 10ml of dialkyl dithiophosphate DDP to stir the suspension to form DDP functionalized liquid metal GLM nano droplets.
The preparation method of the ashless antiwear hydraulic oil comprises the following preparation steps:
Adding 98-99% of base oil by mass into a reaction kettle, stirring, heating to 50-60 ℃ while heating, adding 0.7-1.6% of ashless antiwear hydraulic oil complexing agent by mass and 0.3-0.5% of base oil additive by mass, and keeping stirring at 55-65 ℃ for 5-6 hours until uniformly mixed, thus obtaining the ashless antiwear hydraulic oil.
The following are specific embodiments of the present invention:
description: the raw materials and equipment used in the invention can be purchased commercially.
The invention prepares L-MH46 antiwear hydraulic oil.
Firstly, preparing an ashless antiwear hydraulic oil complexing agent, wherein the ashless antiwear hydraulic oil complexing agent is exemplified by a 1-group formula, and specifically comprises 10% of base oil, 55% of extreme pressure antiwear agent, 5% of rust inhibitor, 12% of antioxidant, 2% of metal passivating agent and 0.3% of anti-emulsifying agent;
The extreme pressure antiwear agent is triphenyl thiophosphate; the antioxidant can be N-phenyl-alpha-aniline; the rust inhibitor is prepared from ethylene butyl diacid and oleic acid glycol ester in a mass ratio of 1:1, and compounding the components according to the proportion. The passivating agent is prepared from a benzotriazole derivative and a methylbenzotriazole derivative according to the mass ratio of 1:1, and compounding the components according to the proportion. The anticoantizer is glycol ester. The base oil is selected from Mobil 150N.
The preparation method of the ashless antiwear hydraulic oil complexing agent comprises the following steps: the components are weighed according to the proportion for standby, then put into a reaction kettle, stirred and heated to 50-60 ℃, kept at 60-70 ℃ and continuously stirred and mixed for 4-6 hours, thus obtaining the ashless antiwear hydraulic oil complexing agent for all the examples.
Secondly, preparing liquid metal nano liquid drops into DDP@GLM. The gallium-based liquid metal nano-droplet can use any one of gallium indium alloy, gallium tin alloy and gallium indium tin alloy, the gallium indium alloy Ga 75.5In24.5 is used for illustration, and the preparation steps comprise:
Fully mixing an equivalent tannic acid TA solution with the concentration of 10mg/ml and a FeCl 3·6H2 O solution with the concentration of 10mg/ml at normal temperature to form a Tannic Acid (TA) -Fe 3+ complex solution, and using the tannic acid TA solution and the FeCl 3·6H2 O complex solution within 20min;
And (3) sucking 300mg of gallium-based liquid metal by using a syringe, injecting the liquid metal into a sample bottle, adding 10ml of Tannic Acid (TA) -Fe 3+ complex solution, treating the solution for 4 hours at normal temperature and normal pressure by using a cell disruption instrument to form a suspension, finally adding 12-14mg of 2-amino-2- (hydroxymethyl) -1, 3-propanediol into the obtained suspension to adjust the pH value to 8-9, and adding 10ml of dialkyl dithiophosphate DDP to stir the mixture to form DDP functionalized liquid metal GLM nano droplets.
The gallium-based liquid metal nano-droplets are subjected to gradient surface modification by utilizing a (TA) -Fe 3+ complex and dithiophosphoric acid dialkyl ester (DDP) to obtain nano-droplets with a core-shell structure, the nano-droplets are uniformly distributed in metallocene poly alpha-olefin base oil to form a continuous nano-droplet protection film, meanwhile, the dithiophosphoric acid dialkyl ester promotes the formation of FeS and FePO 4 protection films, the abrasion of abrasive materials and adhesion is obviously reduced, the bearing capacity of the hydraulic oil is improved from 400N to 1250N, and the low friction coefficient smaller than 0.1 is obtained.
The metallocene polyalphaolefin base oil uses NACOFLOWV600,600 Shanghai Nake.
Example 1
An ashless antiwear hydraulic oil is prepared from base oil (98%), complexing agent (1.6%) and additive (0.4%; wherein, the base oil adopts CTL base oil and metallocene poly alpha olefin base oil with the mass ratio of 4.8:1, mixing to form; the basic oil additive adopts pour point depressant and DDP@GLM according to the mass ratio of 1.2:1, wherein, the pour point depressant is selected from3-301。
The preparation method comprises the following steps: adding base oil into a reaction kettle, stirring, heating to 50-60 ℃, adding an ashless antiwear hydraulic oil complexing agent and a base oil additive, and keeping stirring at 55-65 ℃ for 5-6 hours until the mixture is uniformly mixed, thus obtaining the ashless antiwear hydraulic oil.
Example 2
The difference between this example and example 1 is that the formulation ratio of the hydraulic oil constituting this example is different, specifically as follows: the ashless antiwear hydraulic oil is prepared by adopting 98.5% of base oil, 0.7% of ashless antiwear hydraulic oil complexing agent and 0.5% of base oil additive.
Example 3
The difference between this example and example 1 is that the formulation ratio of the hydraulic oil constituting this example is different, specifically as follows: the ashless antiwear hydraulic oil is prepared by using 99% of base oil, 1.2% of ashless antiwear hydraulic oil complexing agent and 0.3% of base oil additive.
Example 4
The difference between this example and example 3 is that in the base oil of this example, both CTL base oil and metallocene polyalphaolefin base oil are used in a mass ratio of 6.2:1.
Example 5
This example differs from example 3 in that in the base oil of this example, both CTL base oil and metallocene polyalphaolefin base oil are used in a mass ratio of 5.5:1.
Example 6
The difference between this example and example 5 is that, in the base oil additive of this example, both pour point depressant and liquid metal nanodroplets are used in a mass ratio of 1.3:1.
Example 7
The difference between this example and example 5 is that, in the base oil additive of this example, both pour point depressant and liquid metal nanodroplets are used in a mass ratio of 1.4:1.
Example 8
The difference between this example and example 5 is that the pour point depressant is selected from the base oil additives of this example3-302。
Example 9
The difference between this example and example 5 is that the pour point depressant is selected from the base oil additives of this example3-301、/>1-248 According to mass 1:1, compounding.
Comparative example 1
Commercially available ashless antiwear lubricating oil.
Comparative example 2
Comparative example 2 differs from example 1 in that comparative example 2 uses mobil 150N instead of the base oil additive.
Comparative example 3
The comparative example differs from example 1 in that the formulation ratio of the hydraulic oil constituting the present example is not within the range of each formulation ratio of the present invention, specifically as follows: the ashless antiwear hydraulic oil is prepared by adopting 97% of base oil, 2% of ashless antiwear hydraulic oil complexing agent and 0.3% of base oil additive.
Comparative example 4
The comparative example differs from example 1 in that the formulation ratio of the hydraulic oil constituting the present example is not within the range of each formulation ratio of the present invention, specifically as follows: the ashless antiwear hydraulic oil is prepared by using 99% of base oil, 0.5% of ashless antiwear hydraulic oil complexing agent and 0.6% of base oil additive.
Comparative example 5
The difference between this comparative example and example 1 is that the base oil additive of this example does not include DDP@GLM, but only 0.4% pour point depressant is used as the base oil additive.
Performance test:
The performance of the hydraulic oils prepared in examples 1 to 9 of the present application and comparative examples 1 to 5 was examined according to the requirements and test methods in GB11118.1-2011, and the analysis results are shown in tables 1 to 2
Table 1 table for testing the properties of the hydraulic oils prepared in examples 1 to 9
Table 2 the above table of performance tests of the hydraulic oils prepared in comparative examples 1 to 5 is only a preferred example of the present invention, and the present specification should not be construed as limiting the present invention, as the person skilled in the art will vary in specific embodiments and application ranges according to the idea of the present invention.
Claims (7)
1. The ashless antiwear hydraulic oil is characterized by comprising the following components in percentage by mass: 98-99% of base oil, 0.7-1.6% of ashless antiwear hydraulic oil complexing agent and 0.3-0.5% of base oil additive;
Wherein the base oil is a mixture of a CTL base oil and a metallocene polyalphaolefin base oil; the mass ratio of the CTL base oil to the metallocene poly alpha olefin base oil in the base oil is 4.8-6.2:1, a step of;
The ashless antiwear hydraulic oil complexing agent comprises 9-14% of base oil, 50-60% of extreme pressure antiwear agent, 5-8% of antirust agent, 10-20% of antioxidant, 2-4% of metal passivating agent and 0.1-0.8% of emulsifying agent;
The basic oil additive comprises a pour point depressant and liquid metal nano droplets; the liquid metal nano-droplets are DDP@GLM, namely DDP functionalized gallium-based liquid metal nano-droplets.
2. The ashless antiwear hydraulic fluid of claim 1, wherein the mass ratio of CTL base oil to metallocene polyalphaolefin base oil in said base oil is from 5.5 to 6.2:1.
3. The ashless antiwear hydraulic oil of claim 1, wherein in said base oil additive, the mass ratio of said pour point depressant to liquid metal nanodroplets is 1.2 to 1.4:1.
4. The ashless antiwear hydraulic oil of claim 3 wherein said pour point depressant is one or both of VISCOPLEX:3-301, VISCOPLEX:3-302, VISCOPLEX:1-248 in said base oil additive.
5. The ashless antiwear hydraulic fluid of claim 1 wherein said extreme pressure antiwear agent is one or more of triphenyl thiophosphate, tricresyl phosphate, ammonium thiophosphate, aryl phosphate, and amino thiophosphate.
6. The ashless antiwear hydraulic fluid of claim 1 wherein said antioxidant is one or more of N-phenyl- α -aniline, alkyldiphenylamine, 2, 6-di-t-butyl-p-cresol, hindered phenol; the antirust agent is one or more of olefine butyl diacid, oleic acid glycol ester, pentaerythritol monooleate and 1,2, 3-trimethyl benzotriazole; the metal passivating agent is one or more of benzotriazole derivatives, thiadiazole derivatives and methylbenzotriazole derivatives; the anti-emulsifying agent is one or more of glycol ester and polyether polymers; the base oil is at least one of Zhonghai oil 150N and Mobil 150N.
7. The method for preparing the ashless antiwear hydraulic oil according to claim 1, wherein: the preparation method comprises the following preparation steps: adding 98-99% of base oil by mass into a reaction kettle, stirring, heating to 50-60 ℃ while heating, adding 0.7-1.6% of ashless antiwear hydraulic oil complexing agent by mass and 0.3-0.5% of base oil additive by mass, and keeping stirring at 55-65 ℃ for 5-6 hours until uniformly mixed, thus obtaining the ashless antiwear hydraulic oil.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371793A (en) * | 2013-08-15 | 2015-02-25 | 英菲诺姆国际有限公司 | Automotive transmission fluid compositions for improved energy efficiency |
| CN110373248A (en) * | 2019-08-20 | 2019-10-25 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of Nano-Ga base fluid state metal lubrication additive |
| CN110662824A (en) * | 2017-05-30 | 2020-01-07 | 国际壳牌研究有限公司 | Lubricating oil composition for automobile transmission |
| CN112592755A (en) * | 2020-12-14 | 2021-04-02 | 滨州市坤厚工贸有限责任公司 | Efficient ashless hydraulic oil complexing agent composition and preparation method thereof |
| CN115181599A (en) * | 2021-09-28 | 2022-10-14 | 福斯润滑油(中国)有限公司 | Low-temperature composite calcium sulfonate lubricating grease composition and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200339902A1 (en) * | 2019-04-25 | 2020-10-29 | Exxonmobil Research And Engineering Company | Lubricating oil composition and methods for controlling foam tendency and/or foam stability |
-
2023
- 2023-12-14 CN CN202311717179.8A patent/CN117586823B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371793A (en) * | 2013-08-15 | 2015-02-25 | 英菲诺姆国际有限公司 | Automotive transmission fluid compositions for improved energy efficiency |
| CN110662824A (en) * | 2017-05-30 | 2020-01-07 | 国际壳牌研究有限公司 | Lubricating oil composition for automobile transmission |
| CN110373248A (en) * | 2019-08-20 | 2019-10-25 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of Nano-Ga base fluid state metal lubrication additive |
| CN112592755A (en) * | 2020-12-14 | 2021-04-02 | 滨州市坤厚工贸有限责任公司 | Efficient ashless hydraulic oil complexing agent composition and preparation method thereof |
| CN115181599A (en) * | 2021-09-28 | 2022-10-14 | 福斯润滑油(中国)有限公司 | Low-temperature composite calcium sulfonate lubricating grease composition and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Dialkyl dithiophosphate-functionalized gallium-based liquid-metal nanodroplets as lubricant additives for antiwear and friction reduction";Baoluo He等;《ACS Applied Nano Materials》;20200918;全文 * |
| "镓基液态金属的润滑性能研究";李庆林等;《中国优秀硕士论文全文数据库（工程科技I辑）》;20230215;全文 * |
| 镓基液态金属热界面材料的性能研究;高云霞;刘静;王先平;方前锋;;工程热物理学报;20170515(第05期);全文 * |
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