WO2010069986A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2010069986A1
WO2010069986A1 PCT/EP2009/067267 EP2009067267W WO2010069986A1 WO 2010069986 A1 WO2010069986 A1 WO 2010069986A1 EP 2009067267 W EP2009067267 W EP 2009067267W WO 2010069986 A1 WO2010069986 A1 WO 2010069986A1
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Prior art keywords
lubricating oil
oil composition
dithiophosphate
carbons
based anti
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PCT/EP2009/067267
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English (en)
Inventor
Toru Ikai
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Shell Internationale Research Maatschappij B.V.
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Publication of WO2010069986A1 publication Critical patent/WO2010069986A1/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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • 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
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • 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
    • 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
    • C10N2030/10—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
    • C10N2030/20—Colour, e.g. dyes
    • 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
    • C10N2040/08—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
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • This invention relates to a lubricating oil composition.
  • turbine oils are used without change for periods as long as possible, and are also used under severe high-temperature conditions, they require superior heat resistance and oxidative stability.
  • This invention is an attempt to offer a superior lubricating oil composition which has oxidative stability such as to present a sufficiently long oxidation life, little increase in viscosity and excellent energy-saving characteristics, even in cases where it is used in turbine bearings when generating electricity with gas turbines or combined-cycle turbines running in severe high-temperature environments.
  • the present invention provides a superior lubricating oil composition with high oxidative stability and excellent energy conservation with low viscosity increase, by incorporating a phenol-based anti-oxidant represented by the following Formula 1 and an amine-based anti-oxidant in a base oil of a mineral oil and/or a synthetic oil:
  • R 5 and R 6 may be the same or different and each independently represents an alkyl group with from 1 to 4 carbons or a cyclic alkyl group with from 3 to 8 carbons, and R 7 represents an alkylene group with from 1 to 8 carbons.
  • a diphenylamine compound or a phenylnaphthylamine compound it is preferable to use either a diphenylamine compound or a phenylnaphthylamine compound, or a combination thereof.
  • the lubricating oil composition in accordance with this invention acting as a lubricating oil, presents a sufficiently long oxidation life, little increase in viscosity and excellent energy-saving characteristics, even in cases where it is used in turbine bearings when generating electricity with gas turbines or combined- cycle turbines running in severe high-temperature environments. Consequently, the lubricating oil composition of this invention is extremely useful from the standpoint of extending maintenance intervals of turbine bearing units when generating electricity with gas turbines and combined-cycle turbines.
  • base oil of the present lubricating oil composition it is possible to use mineral oils describable as highly refined base oils, and synthetic oils, and oil mixtures thereof, and in particular it is possible to use, singly or as mixtures, base oils which belong to Group I, Group II, Group III, Group IV and so on of the API (American Petroleum Institute) base oil categories.
  • the base oils used here preferably have an elemental sulphur content of less than 700 ppm and preferably less than 500 ppm.
  • the density is preferably from 0.8 to 0.9.
  • the aromatic content is preferably not more than 5% and preferably not more than 3%.
  • Group I base oils include, for example, paraffinic mineral oils obtained by application of a suitable combination of refining processes such as solvent refining, hydrorefining, and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • the viscosity index is typically from 80 to 120 and preferably from 95 to 110.
  • the kinematic viscosity at 40 0 C is preferably from 2 to 680 mmVs and even more preferably from 8 to 220 mm 2 /s.
  • the total sulphur content is typically less than 700 ppm and preferably less than 500 ppm.
  • the total nitrogen content is typically less than 50 ppm and preferably less than 25 ppm.
  • oils with an aniline point of from 80 to 150 0 C, and preferably from 90 to 120 0 C, are typically used.
  • Group II base oils include, for example, paraffinic mineral oils obtained by application 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 is typically from 80 to 120 and preferably from 100 to 120.
  • the kinematic viscosity at 40 0 C is preferably from 2 to 680 mm 2 /s and even more preferably from 8 to 220 mmVs.
  • the total sulphur content is typically less than 300 ppm, preferably less than 200 ppm and even more preferably less than 10 ppm.
  • the total nitrogen content is typically less than 10 ppm and preferably less than 1 ppm.
  • oils with an aniline point of from 80 to 150 0 C, and preferably from 100 to 135°C, are typically used.
  • Suitable Group III base oils 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 Isodewax process which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins, and base oils refined by the Mobil wax isomerisation process. They include those that may be designated as "synthetic oils” according to the rulings of the NAD (National Advertising Division) which is responsible for advertising adjudications in America.
  • the viscosity of these base oils is not specially limited, but the viscosity index is typically from 95 to 145 and preferably from 100 to 140.
  • the kinematic viscosity at 40 0 C is preferably from 2 to 680 rnrnVs and even more preferably from 8 to 220 mm 2 /s.
  • the total sulphur content is typically from 0 to 100 ppm and preferably less than 10 ppm.
  • the total nitrogen content is typically less than 10 ppm and preferably less than 1 ppm.
  • oils with an aniline point of from 80 to 150 0 C, and preferably from 110 to 135°C, are typically used.
  • GTLs gas to liquid oils
  • the viscosity of GTL base oils is not specially limited, but normally the viscosity index is typically from 130 to 180 and preferably from 140 to 175.
  • the kinematic viscosity at 40 0 C is typically from 2 to 680 mm z /s and preferably from 5 to 120 mm 2 /s.
  • the total sulphur content is also 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, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins) and silicone oils.
  • the aforementioned polyolefins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene (1-butene, 2-butene, isobutene) and ot- olefins with five or more carbons. In the manufacture of polyolefins, one kind of the aforementioned olefins may be used singly or two or more kinds may be used in combination. Particularly suitable are the polyolefins called poly- ⁇ -olefins (PAO) . These are base oils of Group IV.
  • PAO poly- ⁇ -olefins
  • the viscosity of these synthetic oils is not specially limited, but the kinematic viscosity at 40 0 C is preferably from 2 to 680 mrti 2 /s and more preferably from 8 to 220 mmVs.
  • 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 composition, is typically at least 60% by mass, preferably at least 70% by mass, more preferably at least 80% by mass, and yet more preferably at least 90% by mass .
  • the viscosity of the aforementioned base oils is not specially limited, but the kinematic viscosity at 40 0 C is preferably from 2 to 680 mmVs and more preferably from 8 to 220 mm 2 /s.
  • the total sulphur content is typically from 0 to 100 ppm and preferably from 0 to 30 ppm.
  • the total nitrogen content is typically from 0 to
  • oils where the aniline point is from 80 to 150 0 C, and preferably from 110 to 135 0 C are typically used.
  • the lubricating oil composition may be made by incorporating phenol-based anti-oxidants and amine-based anti-oxidants in the aforementioned base oils.
  • phenol-based anti-oxidants use is made of those represented by the following Formula 1.
  • R 5 and R 6 may be the same or different and independently represents an alkyl group with from 1 to 4 carbons or a cyclic alkyl group with from 3 to 8 carbons, and R 7 represents an alkylene group with from 1 to 8 carbons.
  • Amine-based anti-oxidants are used in this lubricating oil composition together with the aforementioned phenol-based anti-oxidant .
  • These amine- based anti-oxidants include diphenylamine compounds and phenylnaphthylamine compounds, and these may be used singly or in combination.
  • diphenylamine compounds mention may be made of dialkyldiphenylamine- based compounds, and as examples of phenylnaphthylamine compounds mention may be made of phenyl-ct-naphthylamine- based compounds.
  • dialkyldiphenylamine-based compounds it is preferable to use dialkyldiphenylamines as represented by Formula 3 below.
  • _ Q dialkyldiphenylamines
  • R2 and R3 may be the same or different and each represents an alkyl group of from 1 to 16 carbons.
  • alkyl groups represented by these R2 and R3 mention may be made of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, unde ⁇ yl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and so on (these alkyl groups may be either linear or branched) .
  • branched alkyl groups with from 3 to 16 carbons are preferred for R2 and R3 from the standpoint of superior solubility, and branched alkyl groups with from 3 to 16 carbons derived from olefins of 3 or 4 carbons or oligomers thereof are preferred.
  • olefins of from 3 to 4 carbons mention may be made of propylene, 1-butene, 2-butene and isobutylene, but from the standpoint of solubility propylene or isobutylene is preferred.
  • the alkyl groups denoted by R2 or R3 can each bond at any position of the phenyl group, but the p-position is preferred for amino groups. That is, the dialkyldiphenyl amines represented by the aforementioned Formula 3 are preferably p,p' -dialkyldiphenyl amines.
  • dialkyldiphenyl amines represented by the aforementioned Formula 3 may be used, and synthetics may also be used.
  • the synthetics can easily be synthesised by using a Friedel-Crafts catalyst and reacting a diphenyl amine and an alkyl halide compound of from 1 to 16 carbons, or by reacting a diphenyl amine and an olefin of from 2 to 16 carbons or an oligomer thereof.
  • metal halides as listed in the explanation of the phenyl- ⁇ -napthylaraine-based compounds or acidic catalysts may typically be used.
  • Phenyl- ⁇ -napthylamines as represented by the following Formula 4 are preferred for use as the aforementioned phenyl- ⁇ -napthylamine-based compounds.
  • Rl represents a hydrogen atom or a linear or branched alkyl group with from 1 to 16 carbons.
  • Rl in the aforementioned Formula 4 is an alkyl group
  • this alkyl group will be a linear or a branched alkyl group of froml to 16 carbons.
  • alkyl groups mention may be made of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl. If the number of carbons in Rl were to exceed 16, there would be a risk that the proportion of functional groups in the molecules would become too small and this would have a detrimental effect on the ability to prevent oxidation.
  • Rl in the aforementioned General Formula 4 is an alkyl group, it is preferable from the standpoint of superior solubility if Rl is a branched alkyl group of from 8 to 16 carbons, and it is further preferable if it is a branched alkyl group of from 8 to 16 carbons derived from an oligomer of an olefin of 3 or 4 carbons.
  • olefins with 3 or 4 carbons mention may be made of propylene, 1-butene, 2-butene and isobutylene, but from the standpoint of solubility propylene or isobutylene is preferred.
  • Rl is a branched octyl group derived from a dimer of isobutylene, a branched nonyl group derived from a trimer of propylene, a branched dodecyl group derived from a trimer of isobutylene, a branched dodecyl group derived from a tetramer of propylene or a branched pentadecyl group derived from a pentamer of propylene.
  • a branched octyl group derived from a dimer of isobutylene a branched dodecyl group derived from a trimer of isobutylene or a branched dodecyl group derived from a tetramer of propylene.
  • Rl is an alkyl group, it can bond to the phenyl group at any position but the p-position is preferred.
  • the amino group can bond to any position on the naphthyl group but the ⁇ -position is preferred.
  • Commercial compounds of the phenyl- ⁇ -naphthylamines represented by the aforementioned General Formula (4) may be used, and synthetics may also be used.
  • the synthetics can easily be synthesised by using a Friedel-Crafts catalyst and reacting a phenyl- ⁇ -naphthylamine and an alkyl halide compound of from 1 to 16 carbons, or by reacting a phenyl- ⁇ -naphthylamine and an olefin of from 2 to 16 carbons or an olefin oligomer of from 2 to 16 carbons.
  • metal halides such as aluminium chloride, zinc chloride and iron chloride
  • acidic catalysts such as sulphuric acid, phosphoric acid, phosphorus pentoxide, boron fluoride, acid clays and active clay.
  • the aromatic amine compounds as represented in the aforementioned Formulas (3) and (4) may be used alone as one kind, or may be used as mixtures of two or more kinds with different structures, but, given their ability to maintain the ability to prevent oxidation at high temperatures for longer periods it is preferable to use a 2,2' -alkylenebis (4-alkyl, 6-t-butylphenol) as represented by Formula (1) and a dialkyldiphenylamine as represented by Formula (3) together.
  • the mixing proportion in such case is not limited, but it is preferred if it is in the range of from 1/10 to 10/1 as a mass ratio.
  • the total amount of phenol-based anti-oxidant in the lubricating oil composition of this invention is not specially limited, but in terms of the total amount of the lubricating oil composition it is preferably from
  • the total amount of amine-based anti-oxidant is not specially limited, but in terms of the total amount of the lubricating oil composition it is preferably from
  • the phenol-based anti-oxidant : amine-based anti-oxidant mixing ratio is preferably from 1 : 10 to 10 : 1, more preferably from 1 : 10 to 1 : 1, and even more preferably from 1 : 8 to 1 : 2. If the total content is less than 0.01% by mass, there will be a tendency for the oxidative stability or thermal stability to become unsatisfactory. On the other hand, if it exceeds 10% by mass, the oxidative stability effect obtained will not match the amount incorporated, and it may become a cause of an increase in sludge, which is not desirable.
  • dialkyl-diphenylamines such as p,p' -dloctyl-diphenylamine (Nonflex OD-3, made by Seiko Chemical Ltd), p, p' -di-oc- ⁇ tethylbenzyl-diphenylamine and N-p-butylphenyl-N-p' -octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and monooctyldiphenylamine, bis (dialkylphenyl) amines such as di (2, 4-diethyl ⁇ henyl) amine and di (2-ethyl-4- nonylphenyl ⁇ amine, alkylphenyl-1-naphthylamines such as octyl-phenyl-1-naphthylamine and N-t-dodec
  • Phenol-based anti-oxidants as represented by the aforementioned Formula 1 are used for the phenol-based anti-oxidants, but it is possible to use other phenol- based anti-oxidants together with these.
  • Such 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, 5-di-t-butylhydroquinone (Antage DBH, made by Kawaguchi Chemical Industry Co. Ltd.), t- butylhydroquinone (TBH, made by Seiko Chemical Ltd.
  • 2, 6-di-t-butylphenol, 2, 6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butyl-4-methylphenol and 2, 6-di-t-butyl-4- butylphenol, 2, 6-di
  • polyphenols such as tetrakis [methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl ⁇ propionate] methane (Irganox LlOl, made by Ciba Specialty Chemicals Ltd.), 1, 1, 3-tris (2-methyl-4-hydroxy-5-t- butylphenyl) butane (Yo
  • Phosphorus compounds may also be incorporated in the lubricating oil composition.
  • Such phosphorus compounds include phosphate esters, phosphite esters and derivatives thereof.
  • phosphorus compounds it is possible to use, for example, at least one kind of phosphate esters, phosphite esters, zinc dithiophosphates, dithiophosphate esters or derivatives thereof, or mixtures thereof.
  • phosphate esters mention may be made of tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trlno ⁇ yl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tris (iso-propylphenyl) phosphate, triaryl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate and xylenyldiphenyl phosphate
  • phosphite esters mention may be made of dibutyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphi
  • zinc 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 from 3 to 22 carbons or alkylaryl groups substituted with alkyl groups of from 3 to 18 carbons may be used.
  • zinc dialkyl dithiophosphates mention may be made of zinc dipropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc dipentyl dithiophosphate, zinc dihexyl dithiophosphate, zinc diisope ⁇ tyl 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 dinonylphenyl dithiophosphate, and zinc didodecylphenyl dithiophosphate .
  • dithiophosphate monoalkyl esters such as monopropyl dithiophosphate, monobutyl dithiophosphate, monopentyl dithiophosphate, monohexyl dithiophosphate, monoheptyl dithiophosphate, monooctyl dithiophosphate and monolauryl dithiophosphate (the alkyl groups may be linear or branched) ; dithiophosphate ( (alkyl) aryl) esters such as monophenyl dithiophosphate and monocresyl dithiophosphate; dithiophosphate dialkyl esters such as dipropyl dithiophosphate, dibutyl dithiophosphate, dipentyl dithiophosphate, dihexyl dithiophosphate, diheptyl dithiophosphate, dioctyl dithiophosphate and dilauryl dithiophosphate (the alkyl groups may be linear or branched) ; dithiophosphate di ( ( (
  • phosphate esters and phosphite esters are more preferred because of their superiority in aspects of performance such as further inhibiting sludge, and trialkylphenyl phosphites, and triaryl phosphites such as tricresyl phosphite, monocresyldiphenyl phosphite and dicresylmonophenyl phosphite, are even more preferred.
  • the amount of the aforementioned phosphorus compounds is not specially limited, but, in terms of the total amount of the lubricating oil composition, it is preferably from 0.01 to 5% by mass, more preferably from 0.05 to 4.5% by mass, even more preferably from 0.1 to 4% by mass, yet more preferably from 0.5 to 3.5% by mass, and most preferably from 1 to 3% by mass. If the amount of phosphorus compound is less than 0.01% by mass, there is a risk that the improvement in sludge-inhibiting effect according to the amount of phosphorus compound will be unsatisfactory. On the other hand, if it exceeds 5% by mass, there is a risk that thermal and oxidative stability and foaming properties will be reduced.
  • lubricating oil additives in the lubricating oil composition of this invention.
  • additives mention may be made of: phenol-based and phenothiazine-based antioxidants; acrylate-based defoaming agents such as polyacrylates or siloxane-based defoaming agents such as alkylpolysiloxanes; metal deactivators such as benzotriazoles or derivatives thereof; and pour-point depressants such as polymethacrylates, polyisobutylenes, olefin copolymers and polystyrenes.
  • the amounts when using these additives is not restricted, but, in terms of the total amount of the composition, it is preferable if, in the case of antioxidants, it is from 0.1 to 5% by mass, in the case of defoaming agents from 0.0005 to 1% by mass, in the case of metal deactivators from 0.005 to 1% by mass, and in the case of other additives from 0.1 to 15% by mass in each case.
  • the viscosity of the lubricating oil composition is not specially limited, but the range of kinematic viscosity at 40 0 C is preferably not more than 680 mm 2 /s and more preferably not more than 220 mi ⁇ 2 /s, and also preferably not less than 2 mm 2 /s and more preferably not less than 8 mm 2 /s.
  • the range of kinematic viscosity at 100 0 C is preferably not more than 25 mm 2 /s, more preferably not more than 20 mmVs, yet more preferably not more than 15 mm £ /s and most preferably not more than 10 mm 2 /s, and also preferably not less than 1.0 mm 2 /s, more preferably not less than 1.5 mm 2 /s, yet more preferably not less than 2 its ⁇ Vs and most preferably not less than 2.5 mm 2 /s.
  • the viscosity index of the aforementioned base oil is not specially limited, but is preferably not less than 85, more preferably not less than 100, and yet more preferably not less than 120.
  • Turbine apparatus includes, for example, water turbines, steam turbines and gas turbines, but the lubricating oil composition of this invention exhibits a superior effect when used in combined-cycle turbine apparatus.
  • the outputs of such turbine apparatus are not specially limited.
  • the lubricating oil composition of this invention may be used not only in the aforementioned applications but also preferentially in applications such as hydraulic oils, industrial gear oils, bearing oils and compressor oils. Examples
  • Paraffinic mineral oil of Group II obtained by application 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.
  • refining processes such as hydrorefining and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Additive Al 4, 4' -methylene-bis (2, 6-di-tert- butylphenol) (commercial name: Ionox 220AH ⁇
  • Additive A2 3, 5-di-tert-butyl-hydroxytoluene (BHT)
  • Additive A3 Octyl-3- (4-hydroxy-3, 5-tert ⁇ butylphenol) propionate (commercial name: Irganox L135, manufactured by Ciba Specialty Chemicals Ltd. )
  • Additive A4 Stearyl-3- (4-hydroxy-3, 5-tert- butylphenyl) propionate (commercial name: AIN-100, manufactured by Adeca Ltd.)
  • Additive A5 2, 2' -methylene-bis- (4-ethyl-6--tert- butylphenol) (compound of Formula 2) (commercial name: Nonflex EBP, manufactured by Seiko Chemical Ltd.)
  • Additive B Phosphorus-based anti-oxidant (commercial name: Irgafos 168, manufactured by Ciba Specialty Chemicals Ltd.)
  • Additive C Amine-based anti-oxidant (commercial name: Irganox L57, manufactured by Ciba Specialty Chemicals Ltd. )
  • Additive D Benzotriazole-based anti-corrosive (commercial name: Irgamet 39, manufactured by Ciba Specialty Chemicals Ltd. ⁇
  • Additive E Succinic acid ester (commercial name: LZ859, manufactured by Lubrizol Ltd.)
  • the lubricating oil compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were prepared using the aforementioned base oil and additives.
  • the test was done by the method stipulated in the gas turbine oil specification GEK 107395a of the turbine manufacturing company GE.
  • the RPVOT value of the oil treated under the following test conditions was divided by the RPVOT value of fresh oil, to give the RPVOT residue, by the method standardised in JIS K2514.
  • the significance is that the anti-oxidant is less volatile, there is less wear, and the stability is better.
  • Percentage change (%) [(kinematic viscosity of degraded oil) / (kinematic viscosity of fresh oil) ] x 100
  • Examples 1 to 10 are satisfactory in having a modified RPVOT residue of 88 to 99%, and in the ISOT test, too, they are all satisfactory in having a percentage change (%) in 40 0 C kinematic viscosity between fresh oil and the degraded oil after the test of 1 to 4% and an increase in acid number from fresh oil to degraded oil after the test of 0.2 to 0.5 mgKOH/g.
  • Comparative Example 4 was satisfactory in that the percentage change (%) in 4O 0 C kinematic viscosity between fresh oil and the degraded oil after the ISOT test was 5%, and the increase in acid number from fresh oil to oil degraded after the test was 0.4 mg mgKOH/g, but the modified RPVOT residue was not of pass standard, being 61%.

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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 un antioxydant de type phénol représenté par la formule 1 suivante et un antioxydant de type amine dans une huile de base. Dans la formule, R5 et R6 peuvent être identiques ou différents et représentent indépendamment un groupe alkyle ayant 1 à 4 atomes de carbone ou un groupe alkyle cyclique ayant 3 à 8 atomes de carbone et R7 représente un groupe alkylène ayant 1 à 8 atomes de carbone.
PCT/EP2009/067267 2008-12-19 2009-12-16 Composition d'huile lubrifiante WO2010069986A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109477029A (zh) * 2016-08-31 2019-03-15 出光兴产株式会社 真空泵油
WO2019219858A1 (fr) * 2018-05-18 2019-11-21 Shell Internationale Research Maatschappij B.V. Huile pour compresseur à mouvement alternatif
RU2794597C2 (ru) * 2018-05-18 2023-04-24 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Масло для поршневых компрессоров

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140045736A1 (en) * 2011-05-16 2014-02-13 The Lubrizol Corporation Lubricating Compositions For Turbine And Hydraulic Systems With Improved Antioxidancy

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0572866A1 (fr) * 1992-05-30 1993-12-08 Fuchs Petrolub Ag Oel + Chemie Fluide de travail non-polluant et rapidement biodégradable pour système de lubrification de moteurs et autres éléments de véhicules et de machines
WO2002092735A1 (fr) * 2001-05-11 2002-11-21 Shell International Research Maatschappij B.V. Composition d'huile lubrifiante comprenant une combinaison d'addition composee d'un acide carboxylique et d'une amine en tant qu'agent antirouille
WO2007064843A1 (fr) * 2005-12-02 2007-06-07 Polnox Corporation Compositions d’huile lubrifiante
US20070203035A1 (en) * 2006-02-28 2007-08-30 Jun Dong Stabilizing compositions for lubricants
US20090042753A1 (en) * 2007-08-10 2009-02-12 Marc-Andre Poirier Method for enhancing the oxidation and nitration resistance of natural gas engine oil compositions and such compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5859293A (ja) * 1981-10-02 1983-04-08 Sumitomo Chem Co Ltd 潤滑油用液状酸化防止剤
JP5075343B2 (ja) * 2006-02-20 2012-11-21 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
JP5305589B2 (ja) * 2006-12-25 2013-10-02 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0572866A1 (fr) * 1992-05-30 1993-12-08 Fuchs Petrolub Ag Oel + Chemie Fluide de travail non-polluant et rapidement biodégradable pour système de lubrification de moteurs et autres éléments de véhicules et de machines
WO2002092735A1 (fr) * 2001-05-11 2002-11-21 Shell International Research Maatschappij B.V. Composition d'huile lubrifiante comprenant une combinaison d'addition composee d'un acide carboxylique et d'une amine en tant qu'agent antirouille
WO2007064843A1 (fr) * 2005-12-02 2007-06-07 Polnox Corporation Compositions d’huile lubrifiante
US20070203035A1 (en) * 2006-02-28 2007-08-30 Jun Dong Stabilizing compositions for lubricants
US20090042753A1 (en) * 2007-08-10 2009-02-12 Marc-Andre Poirier Method for enhancing the oxidation and nitration resistance of natural gas engine oil compositions and such compositions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109477029A (zh) * 2016-08-31 2019-03-15 出光兴产株式会社 真空泵油
US11155767B2 (en) 2016-08-31 2021-10-26 Idemitsu Kosan Co., Ltd. Vacuum pump oil
CN109477029B (zh) * 2016-08-31 2022-06-17 出光兴产株式会社 真空泵油
CN114752430A (zh) * 2016-08-31 2022-07-15 出光兴产株式会社 真空泵油
CN114752430B (zh) * 2016-08-31 2023-06-09 出光兴产株式会社 真空泵油
WO2019219858A1 (fr) * 2018-05-18 2019-11-21 Shell Internationale Research Maatschappij B.V. Huile pour compresseur à mouvement alternatif
US11220651B2 (en) 2018-05-18 2022-01-11 Shell Oil Company Reciprocating-type compressor oil
RU2794597C2 (ru) * 2018-05-18 2023-04-24 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Масло для поршневых компрессоров

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