WO2013182565A1 - Composition d'huile de graissage - Google Patents

Composition d'huile de graissage Download PDF

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Publication number
WO2013182565A1
WO2013182565A1 PCT/EP2013/061497 EP2013061497W WO2013182565A1 WO 2013182565 A1 WO2013182565 A1 WO 2013182565A1 EP 2013061497 W EP2013061497 W EP 2013061497W WO 2013182565 A1 WO2013182565 A1 WO 2013182565A1
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Prior art keywords
lubricating oil
oil
oil composition
phosphate
molecular weight
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PCT/EP2013/061497
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English (en)
Inventor
Mitsuhiro Nagakari
Ayano Otsuka
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to US14/404,959 priority Critical patent/US20150119305A1/en
Priority to ES13728157T priority patent/ES2745703T3/es
Priority to RU2014153502A priority patent/RU2642064C2/ru
Priority to DK13728157T priority patent/DK2855645T3/da
Priority to CN201380028149.4A priority patent/CN104334696A/zh
Priority to BR112014030171-9A priority patent/BR112014030171B1/pt
Priority to EP13728157.2A priority patent/EP2855645B1/fr
Publication of WO2013182565A1 publication Critical patent/WO2013182565A1/fr

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    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/017—Specific gravity or density
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/72—Extended drain
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • 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
    • 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
    • C10N2040/135—Steam engines or turbines
    • 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
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention relates to a lubricating oil composition, and specifically relates to a lubricating oil composition which has superior extreme pressure properties, which generates a small amount of sludge and which also has a high viscosity index.
  • the problem to be addressed by the present invention is to offer a lubricating oil composition which has superior extreme pressure properties (ability to prevent welding) , which generates a small amount of sludge and which also has a high viscosity index.
  • the inventors arrived at this invention after discovering that when a copolymer of a specified olefin and an alkyl methacrylate is added in a given fixed range of molecular weights, the amount of sludge generated is reduced, and in addition the viscosity index improves.
  • copolymers of olefins and alkyl In general, copolymers of olefins and alkyl
  • methacrylates are used in lubricating oil compositions as viscosity index improvers, but nothing has been known about reducing the amount of sludge generated.
  • This invention is an attempt to reduce the amount of sludge by adding a copolymer of an olefin and an alkyl methacrylate as an effective constituent to a lubricating oil base oil which contains an extreme pressure agent.
  • the present invention provides a
  • lubricating oil composition comprising (A) 50 to 90% by mass of at least one kind of lubricating oil base oil selected from mineral oils and synthetic oils and (B) 10 to 50% by mass of a copolymer, being of molecular weight 1200 to 50,000, of an olefin and an alkyl methacrylate.
  • Figure 1 shows the molecular weight distribution curves for Additive Al and Additive A2.
  • This invention relates to a lubricating oil
  • composition characterised in that it comprises (A) at least one kind of lubricating oil base oil selected from mineral oils and synthetic oils and (B) a copolymer of an olefin and an alkyl methacrylate of molecular weight within a specified range.
  • the lubricating oil comprises components (A) and (B) , but in particular embodiments the lubricating oil may contain components (A) and (B) or may consist essentially of components (A) and (B) .
  • base oil of the present lubricating oil composition it is possible to use the mineral oils and synthetic oils known as highly refined base oils, and in particular it is possible to use, singly or as mixtures, base oils which belong to Group II, Group III and Group
  • the sulphur content is not more than 300 ppm, but preferably not more than 200 ppm, more preferably not more than 100 ppm, and most preferably not more than 50 ppm.
  • the density is 0.8 to 0.9 g/cm 3 , but preferably 0.8 to 0.865 g/cm 3 , and more preferably 0.81 to 0.83 g/cm 3 .
  • aromatic content aromatic contents in this invention are
  • n-d-M analysis determined by n-d-M analysis in accordance with ASTM D3238 is less than 3%, but preferably less than 2% and more preferably less than 0.1%.
  • Group II base oils As examples of Group II base oils, mention may be made of paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as hydrorefining and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil. Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of not more than 5% and so are suitable for this invention. The viscosity of these base oils is not specially limited, but the viscosity index (viscosity indexes in this invention are determined in accordance with ASTM D2270 and JIS K2283) should be 80 to 120 and preferably 100 to 120.
  • the kinematic viscosity at 40°C should preferably be 2 to 680 mm 2 /s and even more preferably 8 to 220 mm 2 /s.
  • the total sulphur content should be less than 300 ppm, preferably less than 200 ppm and even more preferably less than 10 ppm.
  • the total nitrogen content should be less than 10 ppm and preferably less than 1 ppm.
  • aniline points in this invention are determined in accordance with ASTM D611 and JIS K2256) of 80 to 150°C and preferably 100 to 135°C should be used.
  • Suitable Group III and Group 11+ base oils include paraffinic mineral oils manufactured by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by the Isodewaxing process which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins, and base oils refined by the Mobil wax isomerisation process.
  • the viscosity of these base oils is not specially limited, but the viscosity index should be 95 to 145 and preferably 100 to 140.
  • the kinematic viscosity at 40°C should preferably be 2 to 680 mm 2 /s and even more preferably 8 to 220 mm 2 /s.
  • the total sulphur content should be 0 to 100 ppm and preferably less than 10 ppm.
  • the total nitrogen content should be less than 10 ppm and preferably less than 1 ppm.
  • oils with an aniline point of 80 to 150°C and preferably 110 to 135°C should be used.
  • GTLs gas to liquid synthesised by the Fischer- Tropsch method of converting natural gas to liquid fuel have a very low sulphur content and aromatic content compared with mineral oil base oils refined from crude oil and have a very high paraffin constituent ratio, and so have excellent oxidative stability, and because they also have extremely small evaporation losses, they are suitable as base oils for this invention.
  • the viscosity characteristics of GTL base oils are not specially limited, but normally the viscosity index should be 130 to 180 and preferably 140 to 175. Also, the kinematic viscosity at 40°C should be 2 to 680 mm2/s and preferably 5 to 120 mm2/s.
  • the total sulphur content should also be less than 10 ppm and the total nitrogen content less than 1 ppm.
  • a commercial example of such a GTL base oil is Shell XHVI (registered trademark) .
  • synthetic oils mention may be made of polyolefins, alkylbenzenes , alkylnaphthalenes , esters, polyoxyalkylene glycols, polyphenyl ethers,
  • dialkyldiphenyl ethers dialkyldiphenyl ethers, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins) and silicone oils, or mixtures thereof.
  • polystyrene resins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and -olefins with five or more
  • one kind of the aforementioned olefins may be used singly or two or more kinds may be used in combination.
  • polyalphaolefins PAO
  • base oils of Group IV PAO
  • the polyalphaolefins may also be mixtures of two or more kinds of synthetic oil.
  • the kinematic viscosity at 40°C should be 2 to 680 mm 2 /s, but preferably 20 to 500 mm 2 /s and more preferably 30 to 450 mm 2 /s.
  • the kinematic viscosity at 100°C of said synthetic base oils should be 2 to 100 mm 2 /s, but preferably 4 to 70 mm 2 /s and more preferably 6 to 50 mm 2 /s.
  • the viscosity index of said synthetic base oils should be 110 to 170, but preferably 120 to 160 and more preferably 130 to 155.
  • the 15°C density of said synthetic base oils should be 0.8000 to 0.8600 g/cm 3 , but preferably 0.8100 to 0.8550 g/cm 3 and more preferably 0.8250 to 0.8550 g/cm 3 .
  • the aniline point of said synthetic base oils should be 110 to 180°C, but preferably 120 to 170°C and more preferably 130 to 165°C.
  • the amount of the aforementioned base oil to be incorporated in the lubricating oil composition of this invention is not specially limited, but, taking as a basis the total amount of the lubricating oil
  • a typical range can be given as 50 to 90 wt%, but preferably 50 to 80 wt% and more preferably 50 to 70 wt%.
  • the lower limit of the amount incorporated in the base oil, on the basis of the total amount of the lubricating oil composition should be selected from any of not less than 50, 51, 52, 53, 54, 55, 56, 57, 58 or 59 wt%, and the upper limit of the amount incorporated in the base oil, on the basis of the total amount of the lubricating oil composition, should be selected from any of not more than 67, 68, 69 or 70 wt%.
  • said base oils may also include carboxylic acid ester compounds. These are discussed below.
  • copolymers of olefins and alkyl methacrylates of the present lubricating oil composition mention may be made of copolymers in which the essential constituent monomers are at least one kind of olefin having 2 to 20 carbons and at least one kind of alkyl methacrylate having alkyl groups with 1 to 20 carbons.
  • olefins include various kinds of olefin polymers or hydrides thereof. Any olefin may be used, but as examples mention may be made of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene,
  • alkyl methacrylates having alkyl groups with 1 to 20 carbons mention may be made of:
  • alkyl methacrylates having alkyl groups with 1 to 4 carbons for example, methyl methacrylate, ethyl methacrylate, n- or iso-propyl methacrylate, n-, iso- or sec-butyl methacrylate;
  • alkyl methacrylates having alkyl groups with 8 to 20 carbons for example, n-octyl methacrylate, 2- ethylhexyl methacrylate, n-decyl methacrylate, n-isodecyl methacrylate, n-undecyl methacrylate, n-dodecyl methacrylate, 2-methylundecyl methacrylate, n-tridecyl methacrylate, 2-methyldodecyl methacrylate, n-tetradecyl methacrylate, 2-methyltridecyl methacrylate, n-pentadecyl methacrylate, 2-methyltetradecyl methacrylate, n- hexadecyl methacrylate, and n-octadecyl methacrylate, n- eicosyl methacrylate, n-docosyl methacrylate, n
  • alkyl methacrylates having alkyl groups with 5 to 7 carbons for example, n-pentyl methacrylate and n- hexyl methacrylate.
  • the preferred ones are those belonging to (1) and (2), and the monomers of (2) are further preferred.
  • the preferred monomers of the aforementioned (1) from the standpoint of the viscosity index, are those with 1 to 2 carbons in the alkyl groups.
  • the preferred monomers of the aforementioned (2) from the standpoint of solubility in the base oil and low-temperature characteristics, are those with 10 to 20 carbons in the alkyl groups, and further preferred are those with 12 to 14 carbons.
  • the molecular weight of the aforementioned olefin and alkyl methacrylate copolymers is 1,200 to 80,000, but preferably 1,200 to 50,000 and more preferably 2,000 to 50,000.
  • the weight average molecular weight is 5,000 to 30,000, but preferably 7,000 to 20,000 and more
  • the number average molecular weight is 2,000 to 12,000, but preferably 4,000 to 10,000 and more preferably 5,000 to 9,000.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are those determined by means of gel permeation chromatography (GPC) , and are those obtained by conversion, taking polystyrene as the standard.
  • the aforementioned weight average molecular weight can be regulated by means of the temperature during polymerisation, the monomer concentration (solvent concentration) , the amount of catalyst or the amount of chain transfer agent.
  • the dispersion (Mw/Mn) of the aforementioned olefin and alkyl methacrylate copolymers is 1 to 2.5, but preferably 1.3 to 2.2 and especially 1.7 to 1.9.
  • the viscosity of the aforementioned olefin and alkyl methacrylate copolymers is not specially limited, but the viscosity index should be 100 to 250, but preferably 130 to 220 and more preferably 160 to 200.
  • the kinematic viscosity at 40°C of said copolymers should be 1,000 to 12,000 mm 2 /s, but preferably 2,000 to 10,000 mm 2 /s and more preferably 2,500 to 9,000 mm 2 /s.
  • the kinematic viscosity at 100°C of said copolymers should be 50 to 600 mm 2 /s, but preferably 100 to 500 mm 2 /s and more
  • the 15°C density of said copolymers should be 0.900 to 0.950 g/cm 3 , but preferably 0.910 to 0.940 g/cm 3 and more preferably 0.925 to 0.935 g/cm 3 .
  • copolymers of this invention can be readily obtained by any of the usual methods, and the method of manufacture is not limited.
  • they can be obtained by radical polymerisation using a diluent, olefins and alkyl methacrylates of selected kinds and amounts, a copolymerisation initiator and a chain
  • transfer agent can also be obtained by thermal polymerisation of olefins and alkyl methacrylates of selected kinds and amounts with a diluent.
  • a diluent is optional, but the use of a diluent makes it easier to control the molecular weight of the copolymer. It is also thus often possible to resolve problems to do with handling, because copolymers have viscous
  • Any diluent may be used so long as it an inert hydrocarbon, but it must have solubility properties for the copolymer and lubricating oil.
  • suitable copolymerisation initiators mention may be made of initiators which break down through application of heat and produce free radicals, for instance peroxide compounds such as benzoyl peroxide, t-butyl peroctoate and cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile and 2 , 2 ' -azobis ( 2- methylbutanenitrile ) .
  • peroxide compounds such as benzoyl peroxide, t-butyl peroctoate and cumene hydroperoxide
  • azo compounds such as azobisisobutyronitrile and 2 , 2 ' -azobis ( 2- methylbutanenitrile ) .
  • suitable chain transfer agents mention may be made of those normally used in the art, for instance -styrene dimers,
  • dodecylmercaptan and ethylmercaptan dodecylmercaptan and ethylmercaptan .
  • the use of a chain transfer agent is optional, but the use of a chain transfer agent makes it easier to control the molecular weight of the copolymer.
  • the amount of the aforementioned olefin and alkyl methacrylate copolymer in the lubricating oil composition of this invention is not specially limited, but, taking as a basis the total amount of the lubricating oil composition, a typical range can be given as 10 to 50 wt%, but preferably 10 to 45 wt% and more preferably 15 to 40 wt%.
  • the lower limit of the amount of olefin and alkyl methacrylate copolymer, on the basis of the total amount of the lubricating oil composition, should be selected from any of not less than 10, 11, 12, 13, 14 or 15 wt%, and the upper limit of the amount incorporated in the base oil, on the basis of the total amount of the lubricating oil composition, should be selected from any of not more than 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 wt%.
  • the method of determining the amount of said copolymer within a certain molecular weight range in this case is not specially limited, and can be a value converted theoretically from molecular weight distribution curves.
  • molecular weight distribution curves may be produced by analysing said additives (see, for example, Figure 1) .
  • the molecular weight component of a specified range say, 1200 to
  • copolymer within said specified range and the amount of the component within said specified range in the total additive is calculated on the basis of said molecular weight distribution curves.
  • the aforementioned lubricating oil base oil may contain carboxylic acid ester compounds.
  • carboxylic acid ester compounds mention may be made of polyol esters.
  • polyol esters mention may be made of
  • esters of TMP trimethylolpropane
  • esters of PE penentaerythritol
  • carboxylic acids dicarboxylic acid esters and trimellitic acid esters.
  • the number of carbons in the carboxylic acid residual groups of the ester molecules should also preferably be from 4 to 20 but more preferably from 6 to 18.
  • the amount of the aforementioned carboxylic acid ester incorporated in the lubricating oil composition of this invention is not specially limited, but, taking as a basis the total amount of the lubricating oil
  • a typical range can be given as 5 to 15 wt%, but preferably 7 to 13 wt% and more preferably 8 to 12 wt%.
  • the amount of carboxylic acid ester incorporated, on the basis of the total amount of the lubricating oil composition, should be selected from any of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 wt%.
  • additives other than the aforementioned constituents.
  • anti-oxidants metal deactivators, extreme pressure agents, oiliness improvers, defoaming agents, viscosity index improvers, pour-point depressants, detergent- dispersants, rust preventatives, demulsifying agents, and other lubricating oil additives of the known art.
  • anti-oxidants used in this invention those used in lubricating oils are preferred for practical use, and mention may be made of amine-based anti-oxidants , sulphur-based anti-oxidants , phenol-based anti-oxidants and phosphorus-based anti-oxidants . These anti-oxidants may be used singly or in plural combinations within the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the base oil.
  • dialkyl-diphenylamines such as p, p ' -dioctyl-diphenylamine (Nonflex OD-3, made by Seiko Chemical Ltd), p, p ' -di- -methylbenzyl-diphenylamine and N-p-butylphenyl-N-p ' -octylphenylamine,
  • monoalkyldiphenylamines such as mono-t-butyldiphenylamine and monooctyldiphenylamine, bis (dialkylphenyl ) amines such as di ( 2 , 4-diethylphenyl ) amine and di ( 2-ethyl-4- nonylphenyl ) amine, alkylphenyl-l-naphthylamines such as octyl-phenyl-l-naphthylamine and N-t-dodecylphenyl-1- naphthylamine, 1-naphthylamine, aryl-naphthylamines such as phenyl-l-naphthylamine, phenyl-2-naphthylamine, N- hexylphenyl-2-naphthylamine and N-octylphenyl-2- naphthylamine, phenyl
  • Phenothiazine (made by Hodogaya Chemical Ltd.) and 3,7- dioctylphenothiazine .
  • dialkyl sulphides such as didodecyl sulphide and dioctadecyl sulphide
  • thiodipropionate esters such as didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate and
  • dodecyloctadecyl thiodipropionate and 2- mercaptobenzoimidazole .
  • Phenol-based anti-oxidants include 2-t-butylphenol , 2-t-butyl-4-methylphenol , 2-t-butyl-5-methylphenol , 2,4- di-t-butylphenol , 2 , 4-dimethyl-6-t-butylphenol , 2-t- butyl-4-methoxyphenol , 3-t-butyl-4-methoxyphenol , 2,5-di- t-butylhydroquinone (Antage DBH, made by Kawaguchi
  • bisphenols such as 4,4'- butylidenebis ( 3-methyl-6-t-butylphenol ) (Antage W-300, made by Kawaguchi Chemical Industry Ltd.), 4,4'- methylenebis ( 2 , 6-di-t-butylphenol ) (Ionox 220AH, made by Shell Japan Ltd.), 4 , 4 ' -bis ( 2 , 6-di-t-butylphenol ) , 2,2- (di-p-hydroxyphenyl ) propane (Bisphenol A, made by Shell Japan Ltd.), 2 , 2-bis ( 3 , 5-di-t-butyl-4- hydroxyphenyl ) propane, 4,4' -cyclohexylidenebis (2, 6-t- butylphenol ) , hexamethylene glycol bis [ 3- ( 3 , 5-di-t-butyl-
  • triarylphosphites such as
  • trialkylphosphites such as trioctadecylphosphite and tridecylphosphite, and tridodecyltrithiophosphite .
  • indazole indazole derivatives which are toluindazoles such as 4-alkyl- indazoles and 5-alkyl-indazoles
  • benzothiazole and benzothiazole derivatives which are 2- mercaptobenzothiazole derivatives (Thiolite B-3100, made by Chiyoda Chemical Industries Ltd.) ? 2-
  • alkyldithio benzothiazoles such as 2- (hexyldithio ) benzothiazole and 2-
  • These metal deactivators may be used singly or in plural combinations within the range of 0.01 to 0.5 part by weight relative to 100 parts by weight of the base oil.
  • phosphorus compounds suitable for this invention mention may be made of phosphate esters, acidic phosphate esters, amine salts of acidic phosphate esters, basic phosphate esters, phosphite esters, phosphorothionates , zinc dithiophosphates , esters of dithiophosphoric acid and alkanols or polyether-type alcohols, and derivatives thereof, phosphorus-containing carboxylic acids and phosphorus-containing carboxylic acid esters. These phosphorus compounds may be used singly or in plural combinations within the range of 0.01 to 2 parts by weight relative to 100 parts by weight of the base oil.
  • tributyl phosphate tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl
  • tripentadecyl phosphate trihexadecyl phosphate
  • acidic phosphate esters mention may be made of monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate,
  • amine salts of acidic phosphate esters mention may be made of the methylamine, ethylamine, propylamine, butylamine,
  • phosphite esters mention may be made of dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite,
  • phosphite diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl
  • phosphite triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite and tricresyl phosphite.
  • phosphorothionates mention may be made specifically of tributyl phosphorothionate, tripentyl phosphorothionate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl phosphorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl
  • zinc dialkyl dithiophosphates mention may be made in general of zinc dialkyl dithiophosphates, zinc diaryl dithiophosphates and zinc arylalkyl dithiophosphates.
  • zinc dialkyl dithiophosphates where the alkyl groups of the zinc dialkyl dithiophosphates have primary or secondary alkyl groups of 3 ⁇ 22 carbons or alkylaryl groups substituted with alkyl groups of 3 ⁇ 18 carbons may be used.
  • zinc dialkyl dithiophosphates where the alkyl groups of the zinc dialkyl dithiophosphates have primary or secondary alkyl groups of 3 ⁇ 22 carbons or alkylaryl groups substituted with alkyl groups of 3 ⁇ 18 carbons may be used.
  • zinc dialkyl dithiophosphates where the alkyl groups of the zinc dialkyl dithiophosphates have primary or secondary alkyl groups of 3 ⁇ 22 carbons or alkylaryl groups substituted with alkyl groups of 3 ⁇ 18 carbon
  • dithiophosphates mention may be made of zinc dipropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc dipentyl dithiophosphate, zinc dihexyl dithiophosphate, zinc diisopentyl dithiophosphate, zinc diethylhexyl dithiophosphate, zinc dioctyl dithiophosphate, zinc dinonyl dithiophosphate, zinc didecyl dithiophosphate, zinc didodecyl dithiophosphate, zinc dipropylphenyl dithiophosphate, zinc dipentylphenyl dithiophosphate, zinc dipropylmethylphenyl dithiophosphate, zinc
  • fatty acid esters of polyhydric alcohols in the lubricating oil composition of this invention with a view to improving oiliness.
  • partial or complete esters of saturated or unsaturated fatty acids having 1 - 24 carbons of polyhydric alcohols such as glycerol
  • glycerol esters examples include glycerol
  • sorbitol esters mention may be made of sorbitol monolaurylate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol dilaurylate, sorbitol dipalmitate, sorbitol distearate, sorbitol dioleate, sorbitol tristearate, sorbitol trilaurylate, sorbitol trioleate, and sorbitol tetraoleate.
  • Alkylene glycol esters include ethylene glycol monolaurylate, ethylene glycol monostearate, ethylene glycol monooleate, ethylene glycol dilaurylate, ethylene glycol distearate, ethylene glycol dioleate, propylene glycol monolaurylate, propylene glycol monostearate, propylene glycol monooleate, propylene glycol
  • neopentyl glycol esters mention may be made of neopentyl glycol monolaurylate, neopentyl glycol monostearate, neopentyl glycol monooleate,
  • neopentyl glycol dilaurylate neopentyl glycol distearate and neopentyl glycol dioleate.
  • Trimethylolpropane esters include trimethylolpropane monolaurylate, trimethylolpropane monostearate,
  • Pentaerythritol esters include pentaerythritol monostearate, pentaerythritol monooleate, pentaerythritol dilaurylate, pentaerythritol distearate, pentaerythritol dioleate and
  • dipentaerythritol monooleate dipentaerythritol monooleate.
  • fatty acid esters of polyhydric alcohols it is preferable to use partial esters of polyhydric alcohols and unsaturated fatty acids .
  • pour-point depressants and viscosity-index improvers may also be added to the lubricating oil composition of this
  • viscosity-index improvers examples include non-dispersant type viscosity- index improvers such as polymethacrylates and olefin polymers such as ethylene-propylene copolymers, styrene- diene copolymers, polyisobutylene and polystyrene, and dispersant type viscosity-index improvers where nitrogen- containing monomers have been copolymerised with these, and they may be made with kinds different from the aforementioned copolymers of olefins and alkyl
  • methacrylates As regards the amount to be added, they may be used within the range of 0.05 ⁇ 20 parts by weight relative to 100 parts by weight of the base oil.
  • pour-point depressants mention may be made of polymethacrylate-based polymers. As regards the amount to be added, they may be used within the range of approximately 0.01 ⁇ 5 parts by weight relative to 100 parts by weight of the base oil.
  • Defoaming agents may also be added in order to impart defoaming characteristics to the lubricating oil composition of this invention.
  • defoaming agents suitable for this invention mention may be made of organosilicates such as dimethylpolysiloxane, diethylsilicate and fluorosilicone, and non-silicone type defoaming agents such as polyalkylacrylates .
  • organosilicates such as dimethylpolysiloxane, diethylsilicate and fluorosilicone
  • non-silicone type defoaming agents such as polyalkylacrylates .
  • the amount to be added they may be used singly or in plural combinations within the range of 0.0001 to 0.1 part by weight relative to 100 parts by weight of the base oil.
  • demulsifiers suitable for this invention mention may be made of those in the known art normally used as additives for lubricating oils. As regards the amount to be added, they may be used within the range of 0.0005 to 0.5 part by weight relative to 100 parts by weight of the base oil.
  • the viscosity of the lubricating oil composition of this invention is not specially limited, but the
  • viscosity index should be not less than 130, preferably not less than 140 and more preferably not less than 150.
  • the kinematic viscosity at 40°C of said lubricating oil composition should be 140 to 320 mm 2 /s, but preferably 140 to 200 mm 2 /s and more preferably 140 to 160 mm 2 /s.
  • lubricating oil composition should be not more than 1500 mg/kg, but preferably not more than 1300 mg/kg and more preferably not more than 1200 mg/kg.
  • the RPVOT remainder rate in RPVOT tests on a fresh oil of said lubricating oil composition and the test oil after a Dry TOST test should be not less than 40% but preferably not less than 50% and more preferably not less than 60%.
  • the lubricating oil composition of this invention is used as a machine oil, a hydraulic oil, a turbine oil, a compressor oil, a gear-tooth oil, an oil for sliding surfaces, a bearing oil or a calibration oil.
  • lubricating oil composition of this invention is ideally used as a long drain gear oil.
  • long drain gear oil is an industrial-level gear oil with long intervals between changes of the lubricating oil.
  • the intervals between lubricating oil changes are not specially limited, but typical examples would be not less than one year and preferably not less than 2 years or more preferably not less than 3 years.
  • the lubricating oil composition of this invention is ideally used for the wheels of step-up gearing in apparatus for wind-power generation of
  • PAO Polyalphaolefin
  • Base oil 1 Polyalphaolefin (ordinary name: PA06, characteristics being kinematic viscosity at 40°C: 35.4 mm 2 /s; kinematic viscosity at 100°C: 6.44 mm 2 /s;
  • Base oil 2 Polyalphaolefin (ordinary name: PAO40, characteristics being kinematic viscosity at 40°C: 401 mm 2 /s; kinematic viscosity at 100°C: 40.3 mm 2 /s; viscosity index 151; 15°C density: 0.8491 g/cm 3 ; aniline point: 161°C)
  • Additive A2 Copolymer of olefin and alkyl methacrylate (ordinary name: Viscobase 11-574, made by Evonik Ltd . )
  • Additive A3 Olefin copolymer (ordinary name: Lucant HC-1100, made by Mitsui Chemicals Ltd.)
  • Viscosity index 270
  • Additive A4 Polyisoolefin (ordinary name: Nisseki Polybutene HV300, made by JX Nippon Oil & Energy Corp . )
  • Viscosity index 155
  • Additive B Anglamo is a known gear-oil additives package and it is stated in the Lubrizol catalogue that if 3.25 to 3.9% of this package is blended into the lubricating oil, it will satisfy the API GL-4 standard.
  • the API GL-4 standard is divided into six categories, and the proportion of additives is larger as the number increases, thus increasing the extreme pressure
  • the amount of this Additive B in the formulation was made 2.0% to meet the API GL-3 standard (having extreme pressure properties of at least a medium level), but the amount of Additive B in the formulation is not specially limited.
  • the lubricating oil compositions of Examples of Embodiment 1 to 4 and Comparative Examples 1 to 4 were prepared using the aforementioned constituent materials and using the compositions shown in the Tables.
  • test oil was poured into a container and, without adding any water or catalyst, it was heated for 336 hours by blowing in 3 litres of oxygen every hour in a 120°C constant- temperature tank. 24 hours after completion of the test, the test oil was filtered by means of a membrane filter of 1 pm pore diameter, and the amount of sludge produced was measured.
  • test oil was drawn off into a container, and in the co- presence of 5 ml of distilled water and a copper catalyst it was placed in a bomb pressurised with oxygen at 6.3 kgf/cm 2 at a room temperature of 25°C.
  • the bomb was rotated 100 times a minute inside a 150°C constant- temperature tank.
  • the pressure inside the bomb was recorded, and the time from the maximum pressure reached after introducing the bomb into the constant-temperature tank until a pressure drop of 1.75 kgf/cm 2 was observed was measured, and this value was taken as the RPVOT value.
  • the RPVOT was carried out on fresh oil and on test oil (before filtering) after completion of the TOST.
  • Examples of Embodiment 1 and 2 in which an olefin and alkyl methacrylate copolymer has been used as a viscosity index improver exhibit a high viscosity index of more than 150, and the amount of sludge after the Dry TOST test is less than 1,100 mg/kg.
  • Comparative Example 1 which uses an olefin copolymer, has a high viscosity index but a large amount of sludge.
  • polyisobutylene has little sludge but a low value for the viscosity index.
  • Example of Embodiment 3 and Example of Embodiment 4, which used an olefin and alkyl methacrylate copolymer as a viscosity index improver showed greater improvement of viscosity index and greater reduction in the amount of sludge than Example of Embodiment 1 or Example of Embodiment 2 through the addition of the trihydroxymethylpropyl trioleate. This effect due to the addition of the trihydroxymethylpropyl trioleate is also clear from the difference in the results between
  • Comparative Example 4 can be seen to have a lower

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  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Cette invention a pour objet une composition d'huile de graissage qui a des propriétés extrême-pression (un pouvoir d'empêcher le soudage) supérieures, qui produit une petite quantité de boues et qui également a un indice de viscosité élevé. Ladite composition d'huile de graissage est une composition d'huile de graissage à laquelle un copolymère d'oléfines particulières et de méthacrylates d'alkyle a été ajouté.
PCT/EP2013/061497 2012-06-04 2013-06-04 Composition d'huile de graissage WO2013182565A1 (fr)

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US14/404,959 US20150119305A1 (en) 2012-06-04 2013-06-04 Lubricating oil composition
ES13728157T ES2745703T3 (es) 2012-06-04 2013-06-04 Composición de aceite lubricante
RU2014153502A RU2642064C2 (ru) 2012-06-04 2013-06-04 Композиция смазочного масла
DK13728157T DK2855645T3 (da) 2012-06-04 2013-06-04 Smøreoliesammensætning
CN201380028149.4A CN104334696A (zh) 2012-06-04 2013-06-04 润滑油组合物
BR112014030171-9A BR112014030171B1 (pt) 2012-06-04 2013-06-04 composição de óleo de lubrificação, e, uso de uma composição de óleo de lubrificação
EP13728157.2A EP2855645B1 (fr) 2012-06-04 2013-06-04 Composition d'huile de graissage

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WO2014065984A1 (fr) * 2012-10-24 2014-05-01 Exxonmobil Reearch And Engineering Company Associations de modificateur de viscosité de réserve de base d'huile de graissage à haut indice de viscosité et huiles de graissage issues de celles-ci
RU2726413C2 (ru) * 2015-12-28 2020-07-14 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Композиция смазочного масла для автоматической коробки передач

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JP6130799B2 (ja) * 2014-02-28 2017-05-17 三菱日立パワーシステムズ株式会社 タービン油とタービン組付け油及び該組付け油の製造方法
JP6444219B2 (ja) 2015-02-27 2018-12-26 Ｊｘｔｇエネルギー株式会社 ギヤ油用潤滑油組成物
US10457817B2 (en) 2016-05-02 2019-10-29 Ecolab Usa Inc. 2-mercaptobenzimidazole derivatives as corrosion inhibitors
CN107868691A (zh) * 2016-09-27 2018-04-03 中国石油化工股份有限公司 一种75w‑90黏度级别重负荷车辆齿轮油组合物及其应用
CN107828486B (zh) * 2017-11-25 2020-08-14 北京百思特杰琳科技有限公司 一种润滑油及其制备方法
CN111918954B (zh) * 2018-03-06 2022-11-04 胜牌许可和知识产权有限公司 牵引流体组合物
JP6965441B2 (ja) * 2018-04-26 2021-11-10 トヨタ自動車株式会社 潤滑油組成物

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RU2726413C2 (ru) * 2015-12-28 2020-07-14 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Композиция смазочного масла для автоматической коробки передач
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RU2642064C2 (ru) 2018-01-24
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CN104334696A (zh) 2015-02-04
EP2855645B1 (fr) 2019-08-14

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