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EP1191089B1 - Compositions d'huiles lubrifiantes à faible viscosité - Google Patents

Compositions d'huiles lubrifiantes à faible viscosité Download PDF

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Publication number
EP1191089B1
EP1191089B1 EP01203560A EP01203560A EP1191089B1 EP 1191089 B1 EP1191089 B1 EP 1191089B1 EP 01203560 A EP01203560 A EP 01203560A EP 01203560 A EP01203560 A EP 01203560A EP 1191089 B1 EP1191089 B1 EP 1191089B1
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EP
European Patent Office
Prior art keywords
mass
composition
lubricating oil
oil composition
calcium
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Legal status (The legal status 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 status listed.)
Expired - Lifetime
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EP01203560A
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German (de)
English (en)
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EP1191089A1 (fr
Inventor
Charles Herbert Dr. Bovington
Terence Kelly
Christopher J Locke
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution 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
    • 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
    • C10M2203/108—Residual fractions, e.g. bright stocks
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    • 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
    • C10M2207/027—Neutral salts thereof
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    • 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
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
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    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
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    • 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
    • C10M2223/045—Metal containing thio derivatives
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
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    • 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
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to a low viscosity crankcase lubricant, i.e., SAE J300 classification of 0W or 5W, which exhibits superior performance properties in combustion engines, preferably diesel (compression ignited) engines, especially in heavy duty (HD) diesel engines.
  • lubricants may also be referred to as lubricating oils, lubricating oil compositions, and lubricating oil formulations.
  • the present invention is based on the discovery that low viscosity lubricating oil compositions, such as heavy duty (HD) diesel lubricating oil compositions, can be successfully formulated provided that the base blend viscosity of the components that exhibit Newtonian behaviour is at least 8.2, such as from 8.2 to 30, preferably 8.2 to 10, mm 2 s -1 at 100°C.
  • low viscosity lubricating oil compositions such as heavy duty (HD) diesel lubricating oil compositions
  • the present invention provides a low viscosity lubricating oil composition, preferably a diesel engine lubricating oil composition, more preferably a heavy duty diesel engine lubricating oil composition, having a CCS viscosity less than 3500 mPa.s at -25°C and a sulfated ash value of up to 2.0 mass %, based on the mass of the oil composition, which composition comprises an admixture of:
  • components (c), (d) and (e) can be optional.
  • the present invention provides a method for preparing the lubricating oil composition of the first aspect which comprises the steps of selecting components (a) to (g) so as to provide a composition having a base blend viscosity, as defined in the first aspect, of at least 8.2 mm 2 s -1 at 100°C, and thereafter admixing the components so as to provide a lubricating oil composition having a CCS viscosity of less than 3500 mPa.s at -25°C.
  • the present invention provides a method of lubricating an engine, preferably a diesel engine, especially a heavy duty engine, which comprises supplying to the engine a lubricating oil composition of the first aspect.
  • the present invention provides the use of a lubricating oil composition of the first aspect for meeting the requirements in the M11 cross-head wear engine test.
  • the present invention provides a method of meeting the requirements of the M11 cross-head wear engine test, which comprises using a lubricating oil composition of the first aspect in the test.
  • the term "base blend viscosity" refers to the viscosity, measured according to ASTM D445, of a composition comprising, or an admixture of, components that exhibit Newtonian behaviour, which in the present invention are all the components (including the carrier oil such as the basestock) but excluding the solid polymer or 'active ingredient' of the viscosity modifier, which is considered not to exhibit Newtonian behaviour.
  • the base blend viscosity can refer to the viscosity of a composition comprising the basestock oil, the dispersant, the detergent, the ZDDP, the antioxidant, all carrier oils and diluent oils of the components, the pour depressant and any other components which exhibit Newtonian behaviour, such as anti-foamants.
  • the base blend viscosity parameter is satisfied, and if the CCS viscosity of the lubricating oil composition, which may comprise a viscosity modifier, is less than 3500 mPa.s at -25°C, then the composition will pass the Cummins M11 200 hour cross-head wear test, which satisfies ACEA E5 and API CH-4 specification limits.
  • Computer modeling systems may also be employed to predict the base blend viscosity of a lubricating oil composition based on the viscosity of the components present therein.
  • the additives of the composition may react under the conditions of formulation, storage, or use and that the present invention also extends to the product obtainable or obtained as a result of any such reaction.
  • the oil composition of the present invention has less than 1.5 % of ash, preferably less than 1.25%, especially less than 1 % of ash, such as in the range from 0 to 0.5 % ash, according to method ASTM D874.
  • the amount of phosphorus in the lubricating oil composition is 0 to 0.14 or 0.12, especially less than 0.09, less than 0.08, less than 0.07 or less than 0.06, mass %; more preferably at most 0.05, at most 0.04 or at most 0.03, mass %; such as in the range from 0.001 to 0.03 mass %; for example at most 0.02, or at most 0.01, mass %.
  • the phosphorus content is zero in the lubricating oil composition.
  • the lubricating oil composition contains, independent of the amount of phosphorus, 0 to 2, preferably at most 1.5, such as at most 1, mass %, based on the mass of the oil composition, of sulfur.
  • the amount of sulfur is at most 0.4, at most 0.3 or at most 0.25, mass %; especially at most 0.2, or at most 0.15, mass %; such as in the range from 0.001 to 0.1 mass %.
  • the sulfur content is zero in the lubricating oil composition
  • the amount of elemental phosphorus and sulfur in the lubricating oil composition is measured according to ASTM D5185.
  • the dispersant comprises an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • Dispersants are preferably present in amounts of from 1 to 7, more preferably 1.5 to 6.5, such as 3 to 6 or 5, mass %.
  • the dispersant used in the invention is a polyisobutenyl succinimide dispersant wherein the Mn of the polyisobutenyl groups is from 950 to 3000, such as 900 to 1200 or 2000 to 2300, or a borated derivative thereof which contains not more than 0.2, such as not more than 0.1, for example 0.01 to 0.1, mass % boron, as elemental boron.
  • Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound, such as sulfonic acid, salicylic acid, carboxylic acid, phenol or any derivatives thereof.
  • the metal salt of the organic acid is often referred to as a surfactant.
  • the detergent of the present invention may be a salt of one type of organic acid or a salt of more than one type of organic acid, for example hybrid detergents.
  • the detergent is a salt of one type of organic acid.
  • the proportion of any one type of organic acid to another is not critical.
  • the detergent is selected from the group consisting of a sulfonate, a phenate, a carboxylate, a salicylate, and mixtures thereof.
  • the resulting overbased detergent comprises the neutral detergent (i.e. the metal salt of the organic acid) as the outer layer of a metal base (e.g. carbonate) micelle.
  • a metal base e.g. carbonate
  • Such overbased detergents may have a TBN of 150 or greater, and typically of from 250 to 450 or more.
  • the detergent according to the present invention may be neutral or overbased.
  • neutral and overbased with respect to detergents is well known in the art.
  • At least one of the detergents, whether calcium or magnesium, is an overbased detergent; especially preferred is a calcium overbased detergent.
  • the detergents can have a Total Base Number (TBN) in the range of 15 or 60 to 600, preferably 100 to 450, more preferably 160 to 400. TBN is measured according to ASTM D-2896.
  • Calcium or magnesium phenates are calcium or magnesium salts of phenols and sulfurized phenols and are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide; the neutral or overbased products may be obtained by methods well known in the art.
  • Sulfurised phenols may be prepared by reacting a phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which two or more phenols are bridged by sulfur-containing bridges.
  • Calcium or magnesium sulfonates function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Sulfonates may be prepared from sulfonic acids, which are typically obtained by the sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum, or by the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from 9 to 80 or more, preferably from 16 to 60, carbon atoms per alkyl-substituted aromatic moiety.
  • the oil-soluble sulfonates or alkyl aryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
  • the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 125 to 220 mass % of that stoichiometrically required.
  • the detergent may also be an oil-soluble calcium or magnesium hydrocarbyl substituted salicylate.
  • the hydrocarbyl substituent of the hydrocarbyl-substituted salicylate and their sulphurized derivatives may contain up to 125 aliphatic carbon atoms.
  • substituents include alkyl radicals, for example hexyl, cyclohexyl, octyl, isooctyl, decyl, tridecyl, hexadecyl, eicosyl and tricosyl, radicals derived from the polymerization of both terminal and internal olefins, for example ethene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-butene, 2-pentene, 3-pentene and 4-octene.
  • the hydrocarbyl substituent is one derived from a monoolefin, more preferably from a monoolefin which is either propene, 1-butene or isobutene.
  • the TBN of the calcium or magnesium salicylate may be in the range from 10 to 400.
  • a mixture of two calcium alkyl salicylates having TBN of 50 to 300 such as a TBN of 58 and 160 has been found to be effective in the present invention.
  • Calcium and magnesium salts of carboxylic acids include mono- and dicarboxylic acids.
  • Preferred monocarboxylic acids are those containing 8 to 30 carbon atoms, especially 8 to 24 carbon atoms. (Where this specification indicates the number of carbon atoms in a carboxylic acid, the carbon atom(s) in the carboxylic group(s) is/are included in that number).
  • Examples of monocarboxylic acids are iso-octanoic acid, stearic acid, oleic acid, palmitic acid and behenic acid. Iso-octanoic acid may, if desired, be used in the form of the mixture of C8 acid isomers sold by Exxon Chemical under the trade name "Cekanoic".
  • Suitable acids are those with tertiary substitution at the ⁇ -carbon atom and dicarboxylic acids with 2 or more carbon atoms separating the carboxylic groups. Further, dicarboxylic acids with more than 35 carbon atoms, for example, 36 to 100 carbon atoms, are also suitable. Unsaturated carboxylic acids can be sulphurized.
  • the lubricating oil composition of the present invention has, independent of the amount of elemental magnesium, 0.15 to 0.6, especially 0.25 to 0.55, such as in the range of from 0.4 to 0.55, mass % of elemental calcium, based on the mass of the lubricating oil composition.
  • the lubricating oil composition of the present invention has, independent of the amount of calcium, 0.05 to 0.15, especially 0.05 to 0.1, mass % of elemental magnesium, based on the mass of the lubricating oil composition.
  • the lubricating oil composition has a calcium detergent so that calcium is present in the amount defined above, and optionally a magnesium detergent so that magnesium is present in the amount defined above.
  • At least one detergent especially each detergent, comprises calcium; advantagesously at least one detergent, more advantageously each detergent, is a calcium overbased detergent. Therefore, the amount of calcium detergent corresponds to the amount required for the amount of calcium defined above.
  • the detergent comprises a mixture of a calcium sulfonate and a calcium phenate,or at least one calcium alkyl salicylate. More preferably each detergent is a calcium alkyl salicylate.
  • the phosphorus-containing compound may be metallic (i.e. ash forming) or ashless. Typically such compounds are suitable for anti-wear and anti-oxidant effects.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents.
  • compositions of this invention preferably contain a zinc dihydrocarbyl dithiophosphate (ZDDP), if a phosphorus-containing compound is present, in an amount such that up to 0.16 mass % of phosphorus derived from ZDDP is present in the finished lubricating oil composition.
  • ZDDP zinc dihydrocarbyl dithiophosphate
  • the amount of ZDDP is such as to provide 0 to 0.14 mass % or 0.12 mass % of phosphorus, especially less than 0.09, less than 0.08, less than 0.07 or less than 0.06 mass % of phosphorus; more preferably at most 0.05, at most 0.04 or at most 0.03 mass % of phosphorus; such as in the range from 0.001 to 0.03 mass % of phophorus; for example at most 0.02 or at most 0.01 mass % of phosphorus.
  • the ZDDP may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used, but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
  • the preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms i.e.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • at least 50 mole % of the alcohols used to introduce hydrocarbyl groups into the dithiophosphoric acids are secondary alcohols.
  • the alcohols used to introduce the hydrocarbyl groups may be 60 or 75 mole % secondary. Most preferably, the hydrocarbyl groups are more than 90 mole % secondary. Sulfur- and molybdenum-containing compounds are also examples of anti-wear additives.
  • ashless phosphorus- and sulfur-containing compounds are organophospites and ashless dithiophosphates.
  • the lubricant of this invention may include 0 to 5 or 3, preferably 0.0 to 2.0, mass % of an antioxidant; such as 0.2 or 0.5 to 1.5 mass % of an antioxidant.
  • Suitable compounds include hindered phenols which are oil-soluble phenols substituted at one or both ortho positions, such as the monohydric and mononuclear phenols such as 2,6-di-tertiary alkylphenols (e.g. 2,6-di-t-butylphenol, 2,4,6-tri-t-butyl phenol, 2-t-butyl phenol, 4-alkyl, 2,6-t-butyl phenol, 2,6-di-isopropylphenol, and 2,6-dimethyl, 4-t-butyl phenol).
  • 2,6-di-tertiary alkylphenols e.g. 2,6-di-t-butylphenol, 2,4,6-tri-t-butyl phenol, 2-t-butyl phenol, 4-al
  • hindered phenols include polyhydric and polynuclear phenols such as alkylene-bridged hindered phenols (4,4'-methylenebis(6-tert-butyl-o-cresol), 4,4'-methylenebis(2-tert-amyl-o-cresol), and 2,2'-methylenebis(2,6-di-t-butylphenol).
  • the hindered phenol may be borated or sulfurized.
  • Preferred hindered phenols have good oil-solubility and relatively low volatility.
  • antioxidants which may be used in lubricating oil compositions include oil-soluble copper compounds.
  • the copper may be blended into the oil as any suitable oil-soluble copper compound.
  • oil-soluble it is meant that the compound is oil-soluble under normal blending conditions in the oil or additive package.
  • the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid, for example, a C 8 to C 18 fatty acid, an unsaturated acid, or a branched carboxylic acid.
  • oil-soluble copper dithiocarbamates, sulphonates, phenates, and acetylacetonates are basic, neutral or acidic copper Cu I and/or Cu II salts derived from alkenyl succinic acids or anhydrides.
  • Copper antioxidants will generally be employed in an amount of from about 5 to 500 ppm by weight of the copper, in the final lubricating composition.
  • Metallic dithiocarbamates for example molybdenum dithiocarbamates
  • ashless dithiocarbamates for example molybdenum dithiocarbamates
  • metal dithiophosphates other than zinc
  • organo- sulfur compounds are also examples of antioxidants
  • the antioxidant is an ashless antioxidant.
  • suitable ashless antioxidants also include oil soluble aromatic amines such as C 6 -C 16 dialkyl diphenyl amines, especially dinonyl diphenyl amine.
  • Pour depressants preferably present in an amount of 0.1 to 2 or 1 mass %, otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
  • Such additives are well-known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates. Likewise, the dialkyl fumarate and vinyl acetate may be used as compatibilizing agents.
  • the viscosity modifier functions to impart high and low temperature operability to lubricating oil.
  • the VM used may have that sole function, or may be multifunctional. Multifunctional viscosity modifiers that also function as dispersants are also known.
  • Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
  • Preferred are hydrogenated styrene-isoprene copolymers and hydrogenated isoprene polymers.
  • additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration. It is important to note that addition of the other components noted above must comply with the limitations set forth herein.
  • the viscosity modifier is present in an amount of 0.1 to 1.5 mass % expressed as solid polymer or active ingredient, such as 0.5 to 1.0 mass %, based on the mass of the lubricating oil composition.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
  • Copper- and lead-bearing corrosion inhibitors may be used, but are typically not required with the formulation of the present invention.
  • Typical such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Other additives are the thio and polythio sulfenamides of thiadiazoles. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are preferably present in an amount not exceeding 0.2 mass %.
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1, conveniently 0.001 to 0.05, mass %.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • the oil compositions of this invention can employ a synthetic or mineral oil basestock of lubricating viscosity selected from the group consisting of Group I, II, III, IV and V basestocks and mixtures of thereof.
  • Basestocks may be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
  • API 1509 "Engine Oil Licensing and Certification System” Fourteenth Edition, December 1996 states that all basestocks are divided into five general categories:
  • test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.
  • the basestock can be from Group 1, II, III, IV or V, or any mixture thereof.
  • basestocks suitable in the present invention include basestocks of different viscosities within the same group, for example, a basestock mixture of Group IV having 6 mm 2 s -1 at 100°C and Group IV having 4 mm 2 s -1 at 100°C.
  • the basestock is selected from (a) a Group IV, (b) a Group III, (c) a mixture a Groups IV and V, (d) a mixture of Groups III and IV, (e) a mixture of Groups III and V, (f) mixture of Groups III, IV and IV.
  • the amount of Group V basestock in the mixture is typically up to 30 mass %, based on the mass of the basestock.
  • the basestock can also contain up to 20 mass %, based on the mass of the basestock, of Group 1 and Group II basestocks.
  • the viscosity of the basestock irrespective of whether it is a mixture, can be in the range from 3 to 9, preferably 2.5 to 7.5, more preferably 4.5 to 7, especially from 5 to 6, mm 2 s -1 at 100°C.
  • Group IV basestocks i.e. polyalphaolefins (PAO)
  • PAO polyalphaolefins
  • the polyalphaolefins (PAO) typically have viscosities in the range of 2 to 20 at 100°C.
  • Group IV basestocks having a viscosity of 4 to 8 or 6 mm 2 s -1 at 100°C; or mixtures of Group IV basestocks with up to 80 mass % of Group I, II, III or V basestocks, for example mixtures of Group IV and III and/or V. Also advantageous is a mixture of Group III and V basestocks.
  • Group IV basestocks which have 60 to 75 mass % of a 6 mm 2 s -1 at 100°C PAO and 40 to 25 mass % of a 4 mm 2 s -1 at 100°C PAO as the only basestocks.
  • They may, for example, be oligomers of branched or straight chain alpha-olefins having from 2 to 16 carbon atoms, specific examples being polypropenes, polyisobutenes, poly-1-butenes, poly-1-hexenes, poly-1-octenes and poly-1-decene. Included are homopolymers, interpolymers and mixtures.
  • PAO's are described in "Chemistry and Technology of Lubricants" edited by R. M. Mortier and S. T. Orszulik, published by Blackie (Glasgow) and VCH Publishers Inc. N.Y. (1992): Ch 2 Synthetic base fluids.
  • the lubricating oil composition comprises a polyalphaolefin basestock; a dispersant; a calcium detergent, preferably a calcium alkyl salicylate; a ZDDP; an antioxidant; a pour point depressant; and viscosity modifier, each in an amount as specified herein.
  • each additive When lubricating compositions contain one or more of the above-mentioned additives, each additive has typically been blended into the base oil in an amount which enables the additive to provide its desired function.
  • MASS% (Broad) MASS% (Preferred) (a) Dispersant 1 to 10 1 to 7 (b) Detergent Ca detergent (expressed as Ca) 0.05 to 0.60 0.15 to 0.55 Mg detergent (expressed as Mg) 0.05 to 0.3 0.05 to 0.15 (c) Zinc dihydrocarbyl dithiophosphate (expressed as P) 0 to 0.16 0.03 to 0.14 (d) Anti-oxidant 0 to 3 0 to 2.0 (e) Pour Point Depressant 0 to 2 0.0 to 1.0 (f) Viscosity Modifier (expressed as solid polymer) 0 to 2.0 0.
  • Corrosion Inhibitor 0 to 0.2 0 to 0.1
  • Anti-Foaming Agent 0 to 0.005 0 to 0.004
  • Supplemental Anti-wear Agents 0 to 2.0 0 to 1.5
  • each of the components may be incorporated into a base oil in any convenient way.
  • each of the components can be added directly to the oil by dispersing or dissolving it in the oil at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • all of the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate that is subsequently blended into basestock to make a finished lubricant.
  • Use of such concentrates is conventional.
  • the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of base lubricant.
  • the concentrate additive package is made in accordance with the method described in US-A-4,938,880. That patent describes making a premix of dispersant and metal detergents that is pre-blended at a temperature of at least about 100°C. Thereafter the pre-mix is cooled to at least 85°C and the additional components are added.
  • the final formulations may employ from 2 to 15, preferably 5 to 10, typically 7 to 8, mass % of the additive package(s), the remainder being base oil.
  • compositions Four heavy duty diesel lubricating oil compositions were blended by methods known in the art: two of the compositions (Oils 1 and 2) were of the invention, and two of the compositions (Oils A and B) were comparison oils. Each composition was tested using the M11 engine test (high soot test performance).
  • the graph which plots the crosshead wear results of Oils A, B, 1 and 2, shows that the crosshead wear decreases dramatically as the base-blend viscosity increases from 8.2 mm 2 s -1 and above, thereby demonstrating that the base-blend viscosity is a critical parameter for crosshead wear performance.

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Claims (10)

  1. Composition d'huile lubrifiante à basse viscosité ayant une viscosité CCS inférieure à 3500 mPa.s à -25°C et une teneur en cendre sulfatée d'au plus 2,0 % en masse, par rapport à la masse de la composition d'huile, laquelle composition comprend un mélange de :
    (a) 1 à 10 % en masse d'un dispersant du type polyisobutényl-succinimide dans lequel le Mn des groupes polyisobutényle est de 950 à 3000 ou un dérivé boraté de celui-ci ne contenant pas plus de 0,2 % en masse de bore, par rapport à la masse de la composition d'huile ;
    (b) 0,05 à 0,60 % en masse de calcium élémentaire et/ou 0,05 à 0,30 % en masse de magnésium élémentaire, par rapport à la masse de la composition d'huile, le calcium ou le magnésium, ou bien à la fois le calcium et le magnésium, étant dérivés d'un ou plusieurs détergents ;
    (c) 0 à 0,16 % en masse de phosphore, par rapport à la masse de la composition d'huile ;
    (d) 0 à 5 % en masse d'un antioxydant, par rapport à la masse de la composition d'huile ;
    (e) 0 à 2 % en masse d'un additif abaissant le point d'écoulement, par rapport à la masse de la composition d'huile ;
    (f) 0,1 à 2 % en masse d'un modificateur de viscosité, exprimé en polymère solide, par rapport à la masse de la composition d'huile ; et
    (g) le reste d'une huile lubrifiante de base choisie dans le groupe formé par les huiles de base des Groupes I, II, III, IV, V et tout mélange d'entre elles,
    à condition que lorsque tous les composants choisis parmi (a) à (g) qui présentent un comportement newtonien sont mélangés ensemble, la viscosité du mélange de base présentée par la composition ou le mélange résultant soit d'au moins 8,2 mm2s-1 à 100°C.
  2. Composition selon la revendication 1, dans laquelle le ou chaque détergent est choisi parmi un sulfonate, un phénate, un salicylate, un carboxylate et un mélange d'entre eux.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant (b) est un mélange de détergents consistant en un sulfonate de calcium et un phénate de calcium.
  4. Composition selon l'une quelconque des revendications 1 ou 2, dans laquelle le composant (b) est un détergent du type alkylsalicylate de calcium.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle la viscosité du mélange de base est de 8,2 à 10 mm2s-1 à 100°C.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'huile lubrifiante de base est une poly-alpha-oléfine.
  7. Procédé pour préparer la composition d'huile lubrifiante de l'une quelconque des revendications 1 à 6, comprenant les étapes consistant à choisir les composants (a) à (g) de manière à obtenir une composition ou un mélange ayant une viscosité du mélange de base, telle que définie dans la revendication 1, d'au moins 8,2 mm2s-1 à 100°C, puis mélanger les composants afin d'obtenir une composition d'huile lubrifiante ayant une viscosité CCS inférieure à 3500 mPa.s à -25°C.
  8. Utilisation d'une composition d'huile lubrifiante telle que revendiquée dans l'une quelconque des revendications 1 à 6, pour répondre aux spécifications requises dans le test d'usure de crosse sur moteur M11.
  9. Procédé pour répondre aux spécifications du test d'usure de crosse sur moteur M11, qui comprend l'utilisation dans le test d'une composition d'huile lubrifiante telle que revendiquée dans l'une quelconque des revendications 1 à 6.
  10. Composition d'huile lubrifiante à basse viscosité selon la revendication 1, dans laquelle la composition d'huile lubrifiante est une composition d'huile lubrifiante pour moteur diesel et dans laquelle :
    (a) le dispersant est présent en une quantité de 1 à 7 % en masse et est un dispersant sans cendre ;
    (b) le ou les détergents comprennent un détergent pour huile lubrifiante du type sulfonate, phénate ou salicylate de calcium ou de magnésium, et sont présents en une quantité convenant pour fournir 0,15 à 0,60 % en masse de calcium élémentaire et 0 à 0,15 % en masse de magnésium élémentaire dans la composition ;
    (c) le phosphore est fourni par un dihydrocarbyl-dithiophosphate de zinc présent en une quantité convenant pour fournir 0,03 à 0,16 % en masse de phosphore dans la composition ; et
    (d) l'antioxydant est présent en une quantité de 0 à 3 % en masse et est un antioxydant sans cendre.
EP01203560A 2000-09-25 2001-09-19 Compositions d'huiles lubrifiantes à faible viscosité Expired - Lifetime EP1191089B1 (fr)

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CN101679903B (zh) * 2007-05-10 2014-06-04 卡斯特罗尔有限公司 用于内燃机的含有分散剂添加剂和聚合物分散剂粘度指数改进剂的润滑剂组合物

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EP1323816A1 (fr) * 2001-12-21 2003-07-02 Infineum International Limited Compositions d'huiles lubrifiantes pour moteur diesel de grande puissance

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US5523007A (en) * 1987-07-01 1996-06-04 Ciba-Geigy Corporation Stabilized diesel engine oil
US5525247A (en) * 1993-08-11 1996-06-11 Idemitsu Kosan Co., Ltd. Low ash lubricating oil composition for diesel engine and method for lubrication of diesel engine using same
GB9413976D0 (en) * 1994-07-11 1994-08-31 Exxon Chemical Patents Inc Multigrade lubricating compositions
DE69617761T2 (de) * 1995-02-01 2002-08-08 The Lubrizol Corp., Wickliffe Schmiermittelzusammensetzung mit geringem Aschegehalt
US5558802A (en) * 1995-09-14 1996-09-24 Exxon Chemical Patents Inc Multigrade crankcase lubricants with low temperature pumpability and low volatility
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Publication number Priority date Publication date Assignee Title
CN101679903B (zh) * 2007-05-10 2014-06-04 卡斯特罗尔有限公司 用于内燃机的含有分散剂添加剂和聚合物分散剂粘度指数改进剂的润滑剂组合物

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