WO2007042560A1 - Composition d’huile lubrifiante - Google Patents

Composition d’huile lubrifiante Download PDF

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Publication number
WO2007042560A1
WO2007042560A1 PCT/EP2006/067354 EP2006067354W WO2007042560A1 WO 2007042560 A1 WO2007042560 A1 WO 2007042560A1 EP 2006067354 W EP2006067354 W EP 2006067354W WO 2007042560 A1 WO2007042560 A1 WO 2007042560A1
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WO
WIPO (PCT)
Prior art keywords
group
oil composition
weight
kinematic viscosity
viscosity
Prior art date
Application number
PCT/EP2006/067354
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English (en)
Inventor
Tetsuo Wakizono
Hirohiko Ootsu
Hiroshi Kaneko
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Shell Internationale Research Maatschappij B.V.
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Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2007042560A1 publication Critical patent/WO2007042560A1/fr

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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
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—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 type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • 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
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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

Definitions

  • the present invention relates lubricating oil compositions, in particular to hydraulic oil compositions. More specifically, the present invention relates to a hydraulic oil composition for use in a door closer or a floor hinge employed for opening/closing various types of doors.
  • Door closers using hydraulic oil compositions are widely employed for door opening/closing. Such door closers slowly close a door which has been manually opened, and when the door is caused by a wind or the like to move abruptly, the door closer is required to have the function of slowing down the motion of the door lest it should close on a hand.
  • the door closer fundamentally comprises a cylinder, a piston and an orifice, and prevents the door from being abruptly closed due to the resistance generated by the passage of a hydraulic oil composition through the orifice.
  • mineral oil contains a wax component which is crystallized at low temperature, and such wax crystals grow with time and thereby lower flowability of the oil. As a result, the oil comes to have an increased viscosity or sometimes may even become solidified.
  • a pour-point depressant which is adsorbed on the wax crystals and suppresses the growth of the crystals is generally used; however, there are cases where because of the pour-point depressant the viscosity of the oil does not increase at high temperatures.
  • a typical hydraulic oil composition is a mineral oil or synthetic oil having a low viscosity, which also causes a problem of compatibility with the oil seal.
  • the present invention provides lubricating oil composition, in particular a hydraulic oil composition, comprising a base oil having a kinematic viscosity at
  • the lubricating oil composition has a kinematic viscosity at 40 0 C in the range of from 22 to 95 mm 2 /s; a kinematic viscosity at 100 0 C in the range of from 10 to 30 mm 2 /s; a pour point of -10 0 C or less; a CCS (cold cranking shear) viscosity at -20 0 C of 2500 mPas or less; and a flash point of 140 0 C or more.
  • the polymethacrylate used in the lubricating oil composition of the present invention preferably has a weight average molecular weight in the range of from 150,000 to 700,000.
  • the lubricating oil composition in particular the hydraulic oil composition, is uninfluenced by hot or cold and shows practically the same degree of viscosity whether at low temperature or high temperature and stays in the same condition at all times, thereby making it possible to achieve smooth operation in, for example, a door closer.
  • the lubricating oil composition, in particular the hydraulic oil composition is compatible with oil seals, problems of oil leakage seldom occur even over long periods .
  • the lubricating oil composition of the present invention may be widely employed as hydraulic oil composition of various types.
  • the lubricating oil composition in particular the hydraulic oil composition, has a viscosity index of at least 260.
  • the base oil in the lubricating oil composition of the present invention may be conveniently chosen from mineral oils, synthetic oils and mixtures thereof.
  • Mineral oils that may be conveniently used include base oils manufactured by conducting one or more treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, or hydrorefining on the lubricating oil fraction obtained from the reduced pressure distillation of reduced crude obtained by atmospheric distillation of crude oil.
  • synthetic oils include so-called GTL (gas-to-liquid) base oils obtained by solvent dewaxing or contact dewaxing after synthesis using the Fischer-Tropsch process.
  • GTL gas-to-liquid
  • Other examples of synthetic oils that may be conveniently used include poly- ⁇ -olefins (for example ethylene-propylene copolymers, polybutylenes, 1-octene oligomers, 1-decene oligomers, and hydrides thereof), alkyl benzenes, alkyl naphthalenes, monoesters (for example, butyl stearate or octyl stearate), diesters (for example, ditridecyl glutarate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, dioctyl sebacate, or dioctyl azelate), polyesters (for example, trimellitate
  • the kinematic viscosity at 40 0 C of the base oil is generally in the range of from 2 to 20 mm 2 /s, preferably in the range of from 5 to 15 mm 2 /s.
  • the kinematic viscosity of the base oil exceeds 20 mm 2 /s, when the above polymethacrylate is added, the high-temperature kinematic viscosity of the lubricating oil composition may become too high, or, if polymethacrylate is added in an amount in accordance with the required high-temperature viscosity, the low temperature flowability may become poor due to the base oil failing to reach the necessary viscosity index mentioned below, due to paucity of addition of polymethacrylate .
  • the kinematic viscosity of the base oil is less than 2 mm 2 /s, then the viscosity- increasing effect may become poor at more than a certain added content of the polymethacrylate, even if polymethacrylate is added in accordance with the prescribed high-temperature viscosity, and on the other hand the low-temperature viscosity may become large, with the result that the required low-temperature flowability cannot be obtained, or problems arise regarding safety in that the flash point becomes less than 140 0 C.
  • the viscosity index of the above base oil used in the lubricating oil composition of the present invention is generally 50 or more and preferably 70 or more. If the viscosity index of the base oil is low, then more polymethacrylate must be added in order to obtain the prescribed viscosity index, thereby lowering the solubility of the polymethacrylate at high temperature, with the possible consequence that the target viscosity index may not be achieved.
  • base oils that may be used include normal paraffins, slack wax, GTL wax or a substance of viscosity index about 135 to 180, such as an isoparaffin-based mineral oil obtained by isomerisation .
  • the pour point of the above base oil is generally -10 0 C or less, preferably -20 0 C or less, more preferably -30 0 C or less and most preferably -37.5 0 C or less. If the pour point of the base oil is -10 0 C or less, solidification of the hydraulic oil at low temperature can be prevented.
  • the polymethacrylate that is added to the above base oil may be, for example, a non-dispersion type polymethacrylate or a dispersion type polymethacrylate.
  • Non-dispersion type polymethacrylates include copolymers of one or more monomers selected from compounds expressed by the following general formula (1),
  • Dispersion type polymethacrylates include, for example, copolymers of two or more monomers selected from compounds expressed by the following general formula (4),
  • R 1 represents a hydrogen atom or methyl group and R 2 represents an alkyl group having a carbon number in the range of from 1 to 18.
  • alkyl groups having a carbon number in the range of from 1 to 18 represented by R 2 include: a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group (these alkyl groups may be of straight chain or branched form) .
  • R 3 represents a hydrogen atom or methyl group and R 4 represents a hydrocarbon group having a carbon number in the range of from 1 to 12.
  • hydrocarbon groups having a carbon number in the range of from 1 to 12 represented by R 4 include: alkyl groups such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, or a dodecyl group, (these alkyl groups may be of straight chain or branched form) ; a cycloalkyl group having a carbon number in the range of from 5 to 7 such as a cyclopentyl group, cyclohexyl group, or a cycloheptyl group; an alkyl cycloalkyl group having a carbon number in the range of from 6 to 11 such as a methyl cycl
  • X 1 and X 2 are independently selected from a hydrogen atom, an alkoxy group -OR 10 having a carbon number in the range of from 1 to 18 (wherein R 10 is an alkyl group having a carbon number in the range of from 1 to 18) or a monoalkyl amino group -NHR 11 having a carbon number in the range of from 1 to 18 (wherein R 11 is an alkyl group having a carbon number in the range of from 1 to 18) .
  • R 5 indicates a hydrogen atom or methyl group
  • R 6 indicates an alkylene group having a carbon number in the range of from 1 to 18
  • Y 1 indicates an amine residue or heterocyclic residue containing from 1 to 2 nitrogen atoms and from 0 to 2 oxygen atoms
  • a is 0 or 1.
  • the alkylene group having a carbon number in the range of from 1 to 18 indicated by R 8 may be, for example, an ethylene group, a propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group or octadecylene group (these alkylene groups may be of straight chain or branched form) .
  • the group indicated by Y 1 may be, for example, a dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, anilino group, toluidino group, xylidino group, acetylamino group, benzoylamino group, morpholino group, pyrrolyl group, pyrrolino group, pyridyl group, methyl pyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group or pyrazino group.
  • R 7 indicates a hydrogen atom or methyl group
  • Y 2 indicates an amine residue or heterocyclic residue containing from 1 to 2 nitrogen atoms and from 0 to 2 oxygen atoms .
  • the group indicated by Y 2 may be, for example, a dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, anilino group, toluidino group, xylidino group, acetylamino group, benzoylamino group, morpholino group, pyrrolyl group, pyrrolino group, pyridyl group, methyl pyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group or pyrazino group.
  • Preferred examples of one or more monomers selected from the compounds indicated by general formula (1) to general formula (3) include: alkyl acrylates having a carbon number in the range of from 1 to 18, alkylamide methacrylates having a carbon number in the range of from 1 to 18, olefins having a carbon number in the range of from 2 to 20, styrene, methyl styrene, maleic anhydride esters, maleic anhydride amides and mixtures thereof.
  • Preferred examples of one or more monomers selected from the compounds indicated by general formula (4) and general formula (5) include: dimethylamino methyl methacrylate, diethylamino methyl methacrylate, dimethylamino ethyl methacrylate, 2-methyl-5-vinyl pyridine, morpholino methyl methacrylate, morpholino ethyl methacrylate, N-vinyl pyrrolidone and mixtures thereof .
  • the copolymerisation mol ratio of a copolymer of one or more monomers selected from the compounds indicated by the above general formula (1) to general formula (3) to one or more monomers selected from the compounds indicated by general formula (4) and general formula (5) is typically about 80 : 20 to 95 : 5, respectively.
  • the method of manufacture of said copolymers is not limited, but, a copolymer can conveniently be obtained by radical solvent polymerisation of the monomers in the presence of a polymerisation initiator such as benzoyl peroxide .
  • the weight average molecular weight of the above polymethacrylate is preferably in the range of from 150,000 to 700,000, more preferably in the range of from 200,000 to 500,000, and is preferably selected taking into account the rate of increase of viscosity per unit mass and the rate of improvement of the viscosity index.
  • polymethacrylate is employed in an amount such as to produce a kinematic viscosity at 40 0 C in the range of from 22 to 95 mm 2 /s and may be blended with a suitable amount of one or more compounds selected from the various types of polymethacrylate referred to above. If the kinematic viscosity at 40 0 C is less than 22 mm 2 /s, the high-temperature viscosity is insufficient; on the other hand, if the CCS (cold-cranking shear) viscosity at
  • a suitable content of polymethacrylate is added to the base oil in order to ensure that the kinematic viscosity of the above lubricating oil composition at 40 0 C is within the above range.
  • the amount of polymethacrylate is preferably in the range of from 0.1 to 30 weight%, with reference to the total weight of the lubricating oil composition.
  • the lubricating oil composition of the present invention, apart from the above base oil and polymethacrylate, may be conveniently blended with additional additives, for example, with anti-wear agents, antioxidants, rust inhibitors, corrosion inhibitors and/or anti-foaming agents .
  • Anti-wear agents that may be conveniently used include phosphorus-based compounds, organic molybdenum compounds, fatty acid ester compounds and aliphatic amine based compounds .
  • Examples of phosphorus-based compounds that may be conveniently used include zinc alkyl thiophosphate, phosphoric acid, phosphorous acid, phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triesters, phosphorous acid monoesters, phosphorous acid diesters, phosphorous acid triesters, salts of phosphoric (phosphorous) acid esters, and thiophosphoric acid or thiophosphorous acid and esters thereof, as well as mixtures thereof.
  • phosphorus-based compounds are normally compounds containing a hydrocarbon group having a carbon number in the range of from 2 to 30, preferably in the range of from 3 to 20.
  • hydrocarbon groups having a carbon number in the range of from 2 to 30 there may be mentioned by way of example alkyl groups, cycloalkyl groups, alkyl cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups and arylalkyl groups.
  • alkyl groups there may be mentioned by way of example alkyl groups such as ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, pentadecyl groups and octadecyl groups (these alkyl groups may be of straight chain form or branched form) .
  • alkyl groups such as ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups,
  • cycloalkyl groups there may be mentioned by way of example cycloalkyl groups having a carbon number in the range of from 5 to 7 such as a cyclopentyl group, cyclohexyl group or cycloheptyl group.
  • alkyl cycloalkyl groups there may be mentioned by way of example alkyl cycloalkyl groups having a carbon number in the range of from 6 to 11 such as a methyl cyclopentyl group, dimethyl cyclopentyl group, methyl ethyl cyclopentyl group, diethyl cyclopentyl group, methyl cyclohexyl group, dimethyl cyclohexyl group, methyl ethyl cyclohexyl group, dimethyl cyclohexyl group, methyl cycloheptyl group, dimethyl cycloheptyl group, methyl ethyl cycloheptyl group and diethyl cycloheptyl group (the position of substitution of the alkyl group into the cycloalkyl group is not limited and may be chosen as required) .
  • alkenyl groups there may be mentioned by way of example alkenyl groups such as butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, dodecenyl groups, tetradecenyl groups, pentadecenyl groups, hexadecenyl groups, heptadecenyl groups, and octadecenyl groups (these alkenyl groups may be of straight chain or branched form and the position of the double bond is not limited and may be chosen as required) .
  • alkenyl groups such as butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, dodecenyl groups, tetradeceny
  • aryl groups there may be mentioned by way of example aryl groups such as phenyl groups and naphthyl groups .
  • alkylaryl groups there may be mentioned by way of example alkylaryl groups having a carbon number in the range of from 7 to 18, such as a tolyl group, xylyl group, ethyl phenyl group, propyl phenyl group, butyl phenyl group, pentyl phenyl group, hexyl phenyl group, heptyl phenyl group, octyl phenyl group, nonyl phenyl group, decyl phenyl group, undecyl phenyl group and dodecyl phenyl group (these alkyl groups may be of straight chain or branched form, and the position of substitution into the aryl group is not limited and may be chosen as required) .
  • arylalkyl groups there may be mentioned by way of example arylalkyl groups having a carbon number in the range of from 7 to 12, such as a benzyl group, phenyl ethyl group, phenyl propyl group, phenyl butyl group, phenyl pentyl group and phenyl hexyl group (these alkyl groups may be of straight chain or branched form) .
  • Preferred phosphorus-based compounds include phosphoric acid; phosphorous acid; zinc alkyl dithiophosphates such as zinc dipropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc dipentyl dithiophosphate, zinc dihexyl dithiophosphate, zinc diheptyl dithiophosphate, or zinc dioctyl dithiophosphate (these alkyl groups may be of straight chain form or branched form) ; monoalkyl esters of phosphoric acid such as monopropyl phosphate, monobutyl phosphate, monopentyl phosphate, monohexyl phosphate, monoheptyl phosphate, or monooctyl phosphate (these alkyl groups may be of straight chain form or branched form); mono (alkyl) aryl esters of phosphoric acid such as monophenyl phosphate and monocresyl phosphate; dialkyl esters of phosphoric acid such as diprop
  • salts of phosphoric (phosphorous) acid esters listed above, salts may be conveniently used which are obtained by reacting a nitrogen-containing compound such as ammonia or an amine compound containing in the molecule a hydrocarbon group having a carbon number in the range of from 1 to 8 or a hydroxyl group- containing hydrocarbon group with for example phosphoric acid monoester, phosphoric acid diester, phosphorous acid monoester, or phosphorous acid diester and neutralising part or all of the remaining acidic hydrogen.
  • a nitrogen-containing compound such as ammonia or an amine compound containing in the molecule a hydrocarbon group having a carbon number in the range of from 1 to 8 or a hydroxyl group- containing hydrocarbon group
  • nitrogen-containing compounds include ammonia; alkylamines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, mono- octylamine, dimethylamine, methyl ethylamine, diethylamine, methyl propylamine, ethyl propylamine, dipropylamine, methyl butylamine, ethyl butylamine, propyl butylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine and dioctylamine (these alkyl groups may be of straight chain form or branched form) ; alkanolamines such as monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, monoheptanolamine, mono-octano
  • Any one or more of the above phosphorus compounds may be blended together in use .
  • Organic molybdenum-based compounds may be conveniently used as the above anti-wear agent .
  • Typical compounds include molybdenum dithiocarbamates, molybdenum dithiophosphates and amine molybdenates . Molybdenum dithiocarbamates are particularly preferred.
  • molybdenum dithiocarbamates examples include compounds of general formula (6)
  • molybdenum dithiophosphates examples include compounds of general formula (7)
  • amine molybdenates examples include compounds of general formula (8)
  • R 12 to R 21 are hydrocarbon groups having a carbon number in the range of from 6 to 18 and may be respectively the same or different.
  • X and Y indicate a sulphur atom or oxygen atom, a ⁇ 3, b ⁇ : 3 and c «3.
  • One of said organic molybdenum-based compounds may be employed in the lubricating oil composition of the present invention. Alternatively, two or more of said organic molybdenum-based compounds may be used therein in combination.
  • the content of said organic molybdenum-based compounds is preferably at least 200 weight ppm, more preferably in the range of from 400 to 2000 weight ppm, and even more preferably in the range of from 600 to 1000 weight ppm.
  • organic molybdenum-based compound is less than 200 weight ppm, then the anti-wear effect may be low; if the content exceeds 2000 weight ppm, the effect of such addition of organic molybdenum-based compounds may become saturated.
  • fatty acid ester compounds and/or aliphatic amine-based compounds of the above anti-wear agent fatty acid esters, aliphatic amine compounds or any desired mixture of these having straight chain or branched hydrocarbon groups having a carbon number in the range of 6 to 30, preferably having a carbon number in the range of 8 to 24 and even more preferably having a carbon number in the range of 10 to 20 may be employed.
  • Examples that may be given of such straight chain or branched hydrocarbon groups having a carbon number in the range of 6 to 30 include: alkyl groups such as a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group and triacontyl group, or alkenyl groups such as a hexenyl group, heptenyl group,
  • esters comprising a fatty acid having a hydrocarbon group as above and an aliphatic monohydric alcohol or an aliphatic polyhydric alcohol.
  • Specific examples of fatty acid esters that may be conveniently used include glycerine mono-oleate, glycerine dioleate, sorbitan mono-oleate and sorbitan dioleate .
  • Specific examples of said aliphatic amine compounds include laurylamine, lauryl diethylamine, lauryl diethanolamine, dodecyl dipropanolamine, palmitylamine, stearylamine, stearyl tetramethylene pentamine, oleylamine, oleyl propylene diamine, oleyl diethanolamine, and N-hydroxyethyl oleyl imidazoline, or amine alkylene oxide addition products such as the N, N- dipolyoxyalkylene-N-alkyl (or alkenyl) (having a carbon number in the range of from 6 to 28) addition products of these aliphatic amine compounds, or so-called acid- modified compounds obtained by reacting monocarboxy
  • a suitable example is N,N-dipolyoxyethylene-N-oleylamine .
  • Examples of the aforementioned anti-rust agents include petroleum sulphonates, alkyl benzene sulphonates, dinonyl naphthalene sulphonate, alkenyl succinic acid esters, and polyhydric alcohol esters.
  • corrosion inhibitors examples include benzotriazole-based, tolyl triazole-based, thiadiazole-based and imidazole-based compounds.
  • the aforementioned oxidation inhibitors include phenyl-based oxidation inhibitors and amine-based oxidation inhibitors.
  • Preferred examples of phenol-based oxidation inhibitors that may be conveniently used in the lubricating oil composition of the present invention include 4, 4 ' -methylene bis (2, 6-di-tert-butyl phenol); 4, 4 '-bis (2, 6-di-tert-butyl phenol), 4, 4 ' -bis (2-methyl-6- tert-butyl phenol); 2, 2 ' -methylene bis ( 4-ethyl-6-tert- butyl phenol); 2, 2 ' -methylene bis ( 4-methyl-6-tert-butyl phenol); 4, 4 ' -butylidene bis (3-methyl-6-tert-butyl phenol); 4, 4 ' -isopropylidene bis (2, 6-di-tert-butyl phenol); 2, 2 ' -methylene bis ( 4-methyl-6-nonyl
  • Examples of amine-based oxidation inhibitors that may be conveniently used in the lubricating oil composition of the present invention include substituted and non- substituted phenyl- ⁇ -naphthylamines, alkyl phenol- ⁇ - naphthylamines, and dialkyl diphenylamines .
  • One or more of the aforementioned oxidation inhibitors may be used in the lubricating oil composition of the present invention.
  • the aforementioned phenol-based oxidation inhibitors and amine-based oxidation inhibitors may be used in combination in the lubricating oil composition of the present invention.
  • antifoaming agents examples include a silicone, fluorosilicone, or fluoroalkyl ether.
  • the present invention further provides the use of the lubricating oil composition of the present invention for lubricating a door closer or a floor hinge.
  • a method of lubricating a door closer or a floor hinge comprising using the lubricating oil composition of the present invention to lubricate said door closer or floor hinge .
  • the lubricating oil composition of the present invention can be conveniently prepared by blending together the base oil having a kinematic viscosity at 40 0 C in the range of from 2 to 20 mm 2 /s and a viscosity index of 50 or more with a polymethacrylate and, optionally, one or more additives as hereinbefore described.
  • the resulting lubricating oil composition had a kinematic viscosity 68.8 mm 2 /s at 40 0 C, a kinetic viscosity of 17.92 mm 2 /s at 100 0 C, a viscosity index of 281, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 1120 mPas, and a flash point of 156 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region.
  • a mineral oil (A) having a kinematic viscosity of 24.98 mm 2 /s at 40 0 C, a kinematic viscosity of 4.64 mm 2 /s at 100 0 C, a flash point of 222 0 C and a viscosity index of 101 was mixed with 63.7 parts by weight of a mineral oil (E) having a kinematic viscosity of 4.22 mm 2 /s at 40 0 C, a kinematic viscosity of 1.51 mm/s at 100 0 C, a flash point of 142 0 C, to obtain a mixed base oil having a kinematic viscosity of 5.93 mm 2 /s at 40 0 C, a kinematic viscosity of 1.89 mm 2 /s at 100 0 C and a viscosity index of 108.
  • This mixed base oil was blended with 16.3 parts by weight of a polymethacrylate (b) having a
  • the resulting lubricating oil composition had a kinematic viscosity of 29.86 mm 2 /s at 40 0 C, a kinematic viscosity of 10.49 mm 2 /s at 100 0 C, a viscosity index of 367, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 1900 mPas, and a flash point of 146 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • EXAMPLE 3 21.3 parts by weight of a mineral oil (B) having a kinematic viscosity of 99.21 mm 2 /s at 40 0 C, a kinematic viscosity of 11.14 mm 2 /s at 100 0 C and a flash point of 268 0 C was mixed with 62.2 parts by weight of a mineral oil (C) of kinematic viscosity of 8.74 mm 2 /s at 40 0 C, kinematic viscosity of 2.23 mm 2 /s at 100 0 C, a flash point 160 0 C and a viscosity index of 41, to obtain a mixed base oil having a kinematic viscosity of 15.1 mm 2 /s at 40 0 C, a kinematic viscosity of 3.22 mm 2 /s at 100 0 C and a viscosity index of 74.
  • B mineral oil having a kinematic viscosity of 99.21 mm 2
  • This mixed base oil was blended with 16 parts by weight of a polymethacrylate (a) of weight average molecular weight 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.3 parts by weight of hindered phenol based oxidation inhibitor, 0.05 parts by weight of a oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • a polymethacrylate a of weight average molecular weight 270,000
  • phosphorus compound TCP tricresyl phosphate
  • hindered phenol based oxidation inhibitor a hindered phenol based oxidation inhibitor
  • a oxyalkyl carboxylic acid ester content 70%
  • antifoaming agent dimethyl siloxane 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • the resulting lubricating oil composition had a kinematic viscosity of 67.4 mm 2 /s at 40 0 C, a kinematic viscosity of 18.0 mm 2 /s at 100 0 C, a viscosity index of 288, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 1080 mPas, and a flash point of 156 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • a mineral oil (A) having a kinematic viscosity of 24.98 mm 2 /s at 40 0 C, a kinematic viscosity of 4.64 mm 2 /s at 100 0 C and a flash point of 222 0 C were mixed with 63 parts by weight of a mineral oil (E) of kinematic viscosity of 4.22 mm 2 /s at 40 0 C, a kinematic viscosity of 1.51 mm 2 /s at 100 0 C, and a flash point of 142 0 C, to obtain a mixed base oil having a kinematic viscosity of 5.93 mm 2 /s at 40 0 C, a kinematic viscosity of 1.89 mm 2 /s at 100 0 C and a viscosity index of 108.
  • A mineral oil having a kinematic viscosity of 24.98 mm 2 /s at 40 0 C, a kinematic vis
  • This mixed base oil was blended with 16.3 parts by weight of polymethacrylate (b) having a weight average molecular weight of 400,000, 0.5 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.2 parts by weight of the organic molybdenum compound molybdenum dialkyl thiophosphate and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • the resulting lubricating oil composition had a kinematic viscosity of 29.39 mm 2 /s at 40 0 C, a kinematic viscosity of 10.53 mm 2 /s at 100 0 C, a viscosity index of 375, a pour point less than -50 0 C, a CCS viscosity at -20 0 C of 1890 mPas, and a flash point of 146 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • EXAMPLE 5 6.5 parts by weight of a mineral oil (B) having a kinematic viscosity of 99.21 mm 2 /s at 40 0 C, a kinematic viscosity of 11.14 mm 2 /s at 100 0 C, a flash point of 268 0 C and a viscosity index of 97 was mixed with 24.4 parts by weight of a mineral oil (C) having a kinematic viscosity of 8.74 mm 2 /s at 40 0 C, a kinematic viscosity of 2.23 mm 2 /s at 100 0 C, a flash point of 160 0 C and a viscosity index of 41, 36.7 parts by weight of "XHVI” oil (“XHVI” is a trade mark for synthetic hydrocarbon base oils sold by the Shell Group) having a kinematic viscosity of 23.6 mm 2 /s at 40 0 C, a kinematic viscosity of 5.51 mm 2
  • This mixed base oil was blended with 24.5 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of an oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • TCP tricresyl
  • the resulting lubricating oil composition had a kinematic viscosity of 28.6 mm 2 /s at 40 0 C, a kinematic viscosity of 10.15 mm 2 /s at 100 0 C, a viscosity index of 314, a pour point -45 0 C, a CCS viscosity at -20 0 C of 1450 mPas, and a flash point of 182 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • TCP tricresyl phosphate
  • the resulting lubricating oil composition had a kinematic viscosity of 71.76 mm 2 /s at 40 0 C, a kinematic viscosity of 21.48 mm 2 /s at 100 0 C, a viscosity index of 323, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 660 mPas, and flash point of 160 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • This mixed base oil was blended with 24.66 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of a oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • TCP tricre
  • the resulting lubricating oil composition had a kinematic viscosity of 80.38 mm 2 /s at 40 0 C, a kinematic viscosity of 24.88 mm 2 /s at 100 0 C, a viscosity index of 335, pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 730 mPas, and a flash point of 150 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • This mixed base oil was blended with 29.83 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • TCP tricresyl
  • the resulting lubricating oil composition had a kinematic viscosity of 88.97 mm 2 /s at 40 0 C, a kinematic viscosity of 8.49 mm 2 /s at 100 0 C, a viscosity index of 347, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 730 mPas, and a flash point of 150 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • a mineral oil (A) having a kinematic viscosity of 24.98 mm 2 /s at 40 0 C, a kinematic viscosity of 4.64 mm 2 /s at 100 0 C, a flash point of 222 0 C and a viscosity index of 101 was mixed with 50.75 parts by weight of a mineral oil (C) having a kinematic viscosity of 8.74 mm 2 /s at 40 0 C, a kinematic viscosity of 2.23 mm 2 /s at 100 0 C, a flash point of 160 0 C and a viscosity index 41, and with 20.3 parts by weight of a mineral oil (D) having a kinematic viscosity of 19.24 mm 2 /s at 40 0 C, a kinematic viscosity of 4.19 mm 2 /s at
  • This mixed base oil was blended with 18.2 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of an oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • TCP tricresyl
  • the resulting lubricating oil composition had a kinematic viscosity of 61.59 mm 2 /s at 40 0 C, a kinematic viscosity of 18.22 mm 2 /s at 100 0 C, a viscosity index of 315, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 660 mPas, and a flash point of 160 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • E mineral oil having a kinematic viscosity of 4.22 mm 2 /s at 40 0 C, a kinematic viscosity of 1.51 mm 2 /s at 100 0 C, and a flash point of 142 0 C
  • This mixed base oil was blended with 24.6 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.5 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 1.0 parts by weight of hindered phenol based oxidation inhibitor, 0.2 parts by weight of the organic molybdenum compound molybdenum dialkyl thiophosphate and 0.001 parts by weight of antifoaming agent dimethyl siloxane .
  • the resulting lubricating oil composition had a kinematic viscosity of 52.16 mm 2 /s at 40 0 C, a kinematic viscosity of 19.58 mm 2 /s at 100 0 C, a viscosity index of 390, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 2350 mPas, and a flash point of 142 0 C.
  • This lubricating oil composition had fully satisfactory properties for use as a hydraulic oil composition for a door closer from the low temperature region to the high temperature region and also showed excellent results in the above oil seal compatibility test.
  • a mineral oil (F) having a kinematic viscosity of 8.66 mm 2 /s at 40 0 C, a kinematic viscosity of 2.19 mm 2 /s at 100 0 C, a flash point of 136 0 C and a viscosity index of 30 was mixed with 20 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti- wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of an oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • the resulting lubricating oil composition had a kinematic viscosity of 53.49 mm 2 /s at 40 0 C, a kinematic viscosity of 7.19 mm 2 /s at 100 0 C, a viscosity index of 339, a pour point of less than -50 0 C, CCS viscosity at -20 0 C of 925 mPas, and a flash point of 128 0 C.
  • a mineral oil (F) having a kinematic viscosity of 8.66 mm 2 /s at 40 0 C, a kinematic viscosity of 2.19 mm 2 /s at 100 0 C, a flash point of 136 0 C and a viscosity index of 30 was mixed with 20 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 400,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti-wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of an oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane.
  • F mineral oil having a kinematic viscosity of 8.66 mm 2 /s at 40 0 C, a kinematic viscosity of 2.19 mm 2 /s at 100
  • the resulting lubricating oil composition had a kinematic viscosity of 55.32 mm 2 /s at 40 0 C, a kinematic viscosity of 15.9 mm 2 /s at 100 0 C, a viscosity index of 304, a pour point less than -50 0 C, a CCS viscosity at -20 0 C of 810 mPas, and a flash point of 128 0 C.
  • the resulting lubricating oil composition had a kinematic viscosity of 58 mm 2 /s at 40 0 C, a kinematic viscosity of 13.81 mm 2 /s at 100 0 C, a viscosity index of 249, a pour point of -45 0 C, a CCS viscosity at -20 0 C of 3050 mPas, and a flash point 128 0 C.
  • a poly- ⁇ -olefin (PAO) having a kinematic viscosity of 34.87 mm 2 /s at 40 0 C, a kinematic viscosity of 6.38 mm 2 /s at 100 degrees, a flash point of 258 0 C and a viscosity index of 136 was mixed with 20 parts by weight of a polymethacrylate (a) having a weight average molecular weight of 270,000, 0.2 parts by weight of the phosphorus compound TCP (tricresyl phosphate) as anti-wear agent, 0.3 parts by weight of a hindered phenol based oxidation inhibitor, 0.05 parts by weight of an oxyalkyl carboxylic acid ester (content 70%) and 0.001 parts by weight of antifoaming agent dimethyl siloxane .
  • PAO poly- ⁇ -olefin
  • the resulting lubricating oil composition kinematic viscosity of 93.31 mm 2 /s at 40 0 C, a kinematic viscosity of 22.48 mm 2 /s at 100 0 C, a viscosity index of 270, a pour point of less than -50 0 C, a CCS viscosity at -20 0 C of 3450 mPas, and a flash point of 250 0 C.
  • This lubricating oil composition had a high CCS viscosity at -20 0 C, and produced shrinkage of the oil seal, and was therefore unsuitable for use as hydraulic oil composition for a door closer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une composition d’huile lubrifiante comprenant une huile de base ayant une viscosité cinématique à 40 °C dans la gamme de 2 à 20 mm2/s et un indice de viscosité supérieur ou égal à 50 et un polyméthacrylate, la composition d’huile lubrifiante ayant une viscosité cinématique à 40 °C dans la gamme de 22 à 95 mm2/s ; une viscosité cinématique à 100 °C dans la gamme de 10 à 30 mm2/s ; un point d’écoulement inférieur ou égal à -10 °C ; une viscosité dans un simulateur de démarrage à froid à -20 °C inférieure ou égale à 2500 mPa.s ; et un point éclair supérieur ou égal à 140 °C.
PCT/EP2006/067354 2005-10-13 2006-10-12 Composition d’huile lubrifiante WO2007042560A1 (fr)

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WO2010021643A2 (fr) * 2008-03-31 2010-02-25 Exxonmobil Research And Engineering Company Formulation d'huile hydraulique et procédé pour améliorer le gonflement d’étanchéité
WO2017191215A1 (fr) * 2016-05-04 2017-11-09 Total Marketing Services Composition hydraulique grand froid
CN108841438A (zh) * 2018-07-26 2018-11-20 中国石油化工股份有限公司 闭门器油组合物及其用途
FR3072969A1 (fr) * 2017-10-31 2019-05-03 Total Marketing Services Composition lubrifiante grand froid

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KR101122305B1 (ko) 2007-04-16 2012-03-21 가부시키가이샤 아루박 질량 분석계의 제어 방법 및 질량 분석계
JP5301226B2 (ja) * 2007-09-26 2013-09-25 昭和シェル石油株式会社 建設機械用作動油
JP5564166B2 (ja) * 2008-05-16 2014-07-30 Ｊｘ日鉱日石エネルギー株式会社 潤滑油添加剤組成物、潤滑油添加剤組成物の製造方法、及び潤滑油組成物の製造方法
JP5689326B2 (ja) * 2010-01-25 2015-03-25 昭和シェル石油株式会社 潤滑油組成物の製造方法及び潤滑油組成物用流動性向上剤の選択方法
JP7104576B2 (ja) * 2018-07-03 2022-07-21 Ｅｎｅｏｓ株式会社 潤滑油組成物

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WO2001079399A1 (fr) * 2000-04-13 2001-10-25 Ashland Inc. Lubrifiant de moteur et additif

Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2010021643A2 (fr) * 2008-03-31 2010-02-25 Exxonmobil Research And Engineering Company Formulation d'huile hydraulique et procédé pour améliorer le gonflement d’étanchéité
WO2010021643A3 (fr) * 2008-03-31 2010-06-17 Exxonmobil Research And Engineering Company Formulation d'huile hydraulique et procédé pour améliorer le gonflement d’étanchéité
WO2017191215A1 (fr) * 2016-05-04 2017-11-09 Total Marketing Services Composition hydraulique grand froid
FR3050996A1 (fr) * 2016-05-04 2017-11-10 Total Marketing Services Composition hydraulique grand froid
FR3072969A1 (fr) * 2017-10-31 2019-05-03 Total Marketing Services Composition lubrifiante grand froid
WO2019086423A1 (fr) * 2017-10-31 2019-05-09 Total Marketing Services Composition hydraulique grand froid
CN111433332A (zh) * 2017-10-31 2020-07-17 道达尔销售服务公司 用于极冷的液压组合物
US11434446B2 (en) 2017-10-31 2022-09-06 Total Marketing Services Hydraulic composition for extreme cold
CN108841438A (zh) * 2018-07-26 2018-11-20 中国石油化工股份有限公司 闭门器油组合物及其用途

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