EP1538193B1 - Compositions d'huiles lubrifiantes - Google Patents

Compositions d'huiles lubrifiantes Download PDF

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Publication number
EP1538193B1
EP1538193B1 EP04256985.5A EP04256985A EP1538193B1 EP 1538193 B1 EP1538193 B1 EP 1538193B1 EP 04256985 A EP04256985 A EP 04256985A EP 1538193 B1 EP1538193 B1 EP 1538193B1
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EP
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Prior art keywords
lubricating oil
oil composition
molecular weight
dispersant
ethylene
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EP04256985.5A
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German (de)
English (en)
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EP1538193A1 (fr
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Antonio Gutierrez
Jacob Emert
Andrew J. D. Ritchie
Michael Minotti
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • 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
    • 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
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2215/24—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
    • C10M2217/06—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
    • 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
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C10N2030/041—Soot induced viscosity control
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/41—Chlorine free or low chlorine content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/44—Boron free or low content boron compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/09—Treatment with nitrogen containing compounds

Definitions

  • the present invention relates to lubricating oil compositions. More specifically, the present invention is directed to lubricating oil compositions that provide improved lubricant performance in highly sooted environments, such as those present in heavy duty diesel (HDD) engines provided with exhaust gas recirculation (EGR) systems.
  • HDD heavy duty diesel
  • EGR exhaust gas recirculation
  • EGR exhaust gas recirculation
  • Diesel fuel contains sulfur. Even “low-sulfur” diesel fuel contains 300 to 400 ppm of sulfur. When the fuel is burned in the engine, this sulfur is converted to SO x . In addition, one of the major by-products of the combustion of a hydrocarbon fuel is water vapor. Therefore, the exhaust stream contains some level of NO x , SO x and water vapor. In the past, the presence of these substances has not been problematic because the exhaust gases remained extremely hot, and these components were exhausted in a disassociated, gaseous state.
  • soot levels in lubricating oil compositions build rapidly, and that under said conditions, the kinematic viscosity (kv) of lubricating oil compositions increase to unacceptable levels, even in the presence of relatively small levels of soot (e.g., 3 wt. % soot). Because increased lubricant viscosity adversely affects performance, and can even cause engine failure, the use of an EGR system requires more frequent lubricant replacement. It has been found that the simple addition of an additional amount of dispersant does not adequately address the problem.
  • EP 1387066A describes and claims a heavy duty diesel engine provided with an exhaust gas recirculation system in which intake air and/or exhaust gas recirculation streams are cooled to below the dew point for at least 10% of the time said engine is in operation, said engines being lubricated with a lubricating oil composition comprising a major amount of oil of lubricating viscosity, and a minor amount of one or more high molecular weight polymers comprising (i) copolymers of hydrogenated poly(monovinyl aromatic hydrocarbon) and poly (conjugated diene), wherein the hydrogenated poly (monovinyl aromatic hydrocarbon) segment comprises at least 20 wt.% of the copolymer; (ii) olefin copolymers containing alkyl or aryl amine, or amide groups, nitrogen-containing heterocyclic groups or ester linkages and/or (iii) acrylate or alkylacrylate copolymer derivatives having dispersing groups.
  • EP 1398365A describes and claims a lubricating oil composition having a sulfur content of less than 0.3 wt.%, said lubricating oil composition comprising:
  • the present invention provides a lubricating oil composition as specified in claim 1 of the set of claims following the present description.
  • a lubricating oil composition comprising a major amount of at least one of a Group I, Group II and/or Group III mineral oil of lubricating viscosity; a minor amount of one or more high molecular weight polymers and a minor amount of dispersant as defined in present claim 1.
  • dispersants that are the reaction product of a polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester and a polyamine; at least one nitrogen-containing dispersant having a polyalkenyl moiety with a number average molecular weight of at least about 1800, and from about 1.3 to 1.7 mono- or dicarboxylic acid producing moieties per polyalkenyl moiety; the one or more nitrogen-containing dispersants contributing at least 0.08 wt. % of nitrogen to the lubricating oil composition.
  • the high molecular weight olefin copolymer comprises an ethylene-propylene copolymer grafted with maleic anhydride and derivatized with an aryl amine.
  • a lubricating oil composition as described in the first aspect, wherein the total amount of diaryl amine moieties in the lubricating oil composition is from 0.5 to 5 mmols/kg, with greater than 50% of said diaryl amine moieties being introduced via molecules having a molecular weight of greater than 5000.
  • a lubricating oil composition as described in the first or second aspect, wherein the lubricating oil composition further comprises from 6 to 50 mmols of phenate surfactant per kilogram of finished lubricating oil.
  • a lubricating oil composition as described in the first, second, or third aspect, wherein said dispersant comprises from 1.3 to 1.6 mono- or di-carboxylic acid producing moieties per polyalkenyl moiety, and a boron content of less than 20 ppm.
  • a lubricating oil composition as described in any of the first to fourth aspect, having a sulfated ash content of less than 0.5 wt. %.
  • a lubricating oil composition as in the first aspect, having a sulfur content less than 0.3 wt. %, a sulfated ash content of less than 0.5 wt. %, and a chlorine content of less than 50 ppm.
  • a lubricating oil composition as in any of the first to sixth aspect, wherein the functionalized, high molecular weight olefin molecule is derived from an amorphous ethylene-propylene copolymer, or a blend of an amorphous and a semi-crystalline ethylene-propylene copolymer with an SSI of from 5 to 30, produced by simultaneously shearing and functionalizing higher molecular weight ethylene-propylene copolymers, with maleic anhydride, in an extruder.
  • a method of operating a diesel engine provided with an exhaust gas recirculation system which method comprises lubricating said engine with a lubricating oil composition of any of the first to seventh aspect.
  • oils of lubricating viscosity useful in the practice of the invention may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils.
  • the viscosity of the oil ranges from about 2 mm2/sec (centistokes) to about 40 mm 2 /sec, especially from about 3 mm 2 /sec to about 20 mm 2 /sec, most preferably from about 4 mm 2 /sec to about 10 mm 2 /sec, as measured at 100°C.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • the oil of lubricating viscosity may comprise a Group I, Group II or Group III, base stock or base oil blends of the aforementioned base stocks.
  • the oil of lubricating viscosity is a Group II or Group III base stock, or a mixture thereof, or a mixture of a Group I base stock and one or more a Group II and Group III.
  • the base stock, or base stock blend preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%. Most preferably, the base stock, or base stock blend, has a saturate content of greater than 90%.
  • the oil or oil blend will have a sulfur content of less than 1%, preferably less than 0.6%, most preferably less than 0.3%, by weight.
  • the volatility of the oil or oil blend is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal 16%.
  • the viscosity index (VI) of the oil or oil blend is at least 85, preferably at least 100, most preferably from about 105 to 140.
  • base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 . Said publication categorizes base stocks as follows:
  • High molecular weight polymers are olefin copolymers (OCPs) containing dispersing groups such as alkyl or aryl amine, or amide groups, nitrogen-containing heterocyclic groups or ester linkages.
  • OCPs olefin copolymers
  • the olefin copolymers can comprise any combination of olefin monomers, but are most commonly ethylene and at least one other ⁇ -olefin.
  • the at least one other ⁇ -olefin monomer is conventionally an ⁇ -olefin having 3 to 18 carbon atoms, and is most preferably propylene.
  • copolymers of ethylene and higher ⁇ -olefins, such as propylene often include other polymerizable monomers. Typical of these other monomers are non-conjugated dienes such as the following, non-limiting examples:
  • dienes containing at least one of the double bonds in a strained ring are preferred.
  • the most preferred diene is 5-ethylidene-2-norbornene (ENB).
  • ENB 5-ethylidene-2-norbornene
  • the amount of diene (wt. basis) in the copolymer can be from 0% to about 20%, with 0% to about 15% being preferred, and 0% to about 10% being most preferred.
  • the most preferred olefin copolymer is ethylene-propylene.
  • the average ethylene content of the copolymer can be as low as 20% on a weight basis.
  • the preferred minimum ethylene content is about 25%. A more preferred minimum is 30%.
  • the maximum ethylene content can be as high as 90% on a weight basis; preferably the maximum ethylene content is 85%, most preferably about 80%.
  • the olefin copolymers contain from about 35 to 75 wt. % ethylene, more preferably from about 40 to about 70 wt. % of ethylene.
  • Ethylene-propylene copolymers having an ethylene content of up to about 55 wt. % are considered amorphous; such copolymers having higher ethylene contents are referred to as semi-crystalline.
  • Ethylene content of ethylene-propylene can generally be measured using the procedure of ASTM-D3900.
  • Polymer molecular weight, specifically, M n can be determined by various known techniques.
  • One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979 ).
  • GPC gel permeation chromatography
  • Another useful method for determining molecular weight, particularly for lower molecular weight polymers is vapor pressure osmometry (see, e.g., ASTM D3592).
  • Lubricating oil compositions useful in the practice of the present invention contain the high molecular weight olefin copolymers (OCPs) containing dispersing groups in an amount of from 0.10 to 2 wt. %, based on polymer weight; more preferably from 0.2 to 1 wt. %, most preferably from 0.3 to 0.8 wt. %. Said components are present in an amount providing from 0.0003 to 0.008 wt. % of nitrogen to the lubricating oil composition.
  • OCPs high molecular weight olefin copolymers
  • the percentage of polymer chains exhibiting terminal ethenylidene unsaturation may be determined by FTIR spectroscopic analysis, titration, or C 13 NMR.
  • the chain length of the R 1 alkyl group will vary depending on the comonomer(s) selected for use in the polymerization.
  • Mixtures of monounsaturated carboxylic materials (i) - (iv) also may be used.
  • the monounsaturation of the monounsaturated carboxylic reactant becomes saturated.
  • maleic anhydride becomes backbone-substituted succinic anhydride
  • acrylic acid becomes backbone-substituted propionic acid.
  • Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with a long hydrophobic tail.
  • the polar head comprises a metal salt of an acidic organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to 80.
  • a large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • Such overbased detergents may have a TBN of 150 or greater, and typically will have
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from 20 to 450. Combinations of detergents, whether overbased or neutral or both, may be used.
  • 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 included 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 about 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
  • Carboxylate detergents e.g., salicylates
  • an aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen.
  • the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example benzene is a preferred moiety.
  • the aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.
  • the carboxylic moiety may be attached directly or indirectly to the aromatic moiety.
  • aromatic carboxylic acids are salicylic acids and sulfurized derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof.
  • Processes for sulfurizing, for example a hydrocarbyl - substituted salicylic acid are known to those skilled in the art.
  • Salicylic acids are typically prepared by carboxylation, for example, by the Kolbe - Schmitt process, of phenoxides, and in that case, will generally be obtained, normally in a diluent, in admixture with uncarboxylated phenol.
  • the detergent used will be a detergent system in which from about 60% to 100% of the total amount of detergent surfactant is phenate and/or salicylate. Phenate neutral and overbased detergents are preferred.
  • lubricating oil compositions useful in the present invention will contain no more than about 30 wt. %, preferably no more than about 20 wt. %, more preferably no more than 5 wt. % sulfonate detergent, based on the total weight of detergent.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidant agents.
  • the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are most commonly used in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight of the lubricating oil composition. They 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
  • Typical oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms.
  • the amines may contain more than two aromatic groups.
  • Compounds having a total of at least three aromatic groups in which two aromatic groups are linked by a covalent bond or by an atom or group (e.g., an oxygen or sulfur atom, or a -CO-, -SO 2 - or alkylene group) and two are directly attached to one amine nitrogen also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen.
  • the aromatic rings are typically substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups.
  • the amount of any such oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen should preferably not exceed 0.4 wt. % active ingredient.
  • lubricating oil compositions in accordance with the present invention contain from about 0.05 to about 5 wt. %, preferably from about 0.10 to about 3 wt. %, most preferably from about 0.20 to about 1.5 wt. % of phenolic antioxidant, based on the total weight of the lubricating oil composition. Even more preferably, lubricating oil compositions in accordance with the present invention contain phenolic antioxidant in the amount set forth above, and comprise less than 0.1 wt. %, based on the total weight of the lubricating oil composition, aromatic amine antioxidant.
  • Friction modifiers and fuel economy agents that are compatible with the other ingredients of the final oil may also be included.
  • examples of such materials include glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine.
  • a preferred lubricating oil composition contains a dispersant composition of the present invention, base oil, and a nitrogen-containing friction modifier.
  • the molybdenum compound may be an acidic molybdenum compound. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
  • organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
  • the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil.
  • the number of carbon atoms in each group will generally range between about 1 to about 100, preferably from about 1 to about 30, and more preferably between about 4 to about 20.
  • Preferred ligands include dialkyldithiophosphate, alkylxanthate, and dialkyldithiocarbamate, and of these dialkyldithiocarbamate is more preferred.
  • Organic ligands containing two or more of the above functionalities are also capable of serving as ligands and binding to one or more of the cores. Those skilled in the art will realize that formation of the compounds of the present invention requires selection of ligands having the appropriate charge to balance the core's charge.
  • a trinuclear molybdenum-sulfur halide salt such as [M'] 2 [Mo 3 S 7 A 6 ], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble or dispersible trinuclear molybdenum compound.
  • the appropriate liquid/solvent may be, for example, aqueous or organic.
  • a compound's oil solubility or dispersibility may be influenced by the number of carbon atoms in the ligand's organo groups. In the compounds of the present invention, at least 21 total carbon atoms should be present among all the ligand's organo groups.
  • the ligand source chosen has a sufficient number of carbon atoms in its organo groups to render the compound soluble or dispersible in the lubricating composition.
  • oil-soluble or “dispersible” used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • the viscosity index of the base stock is increased, or improved, by incorporating therein certain polymeric materials that function as viscosity modifiers (VM) or viscosity index improvers (VII).
  • polymeric materials useful as viscosity modifiers are those having number average molecular weights (Mn) of from about 5,000 to about 250,000, preferably from about 15,000 to about 200,000, more preferably from about 20,000 to about 150,000.
  • the high molecular weight olefin copolymers (OCPs) containing dispersing groups need not comprise the sole VM in the lubricating oil composition, and other VM, such as a hydrogenated styrene-isoprene block copolymer, or non-functionalized olefin copolymer VM may be used in combination therewith.
  • Suitable viscosity modifiers other than the high molecular weight olefin copolymers (OCPs) containing dispersing groups of the invention are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers 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.
  • LOFIs Pour point depressants
  • VM lube oil flow improvers
  • Typical additives that improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, and polymethacrylates.
  • LOFIs can be grafted with grafting materials such as, for example, maleic anhydride, and the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional additives.
  • 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 need not be further elaborated herein.
  • Fully formulated lubricating oil compositions of the present invention preferably have a sulfur content of less than about 0.3 wt. %, preferably less than about 0.25 wt. % more preferably less than about 0.20 wt. %, most preferably less than about 0.15 wt. %.
  • the Noack volatility of the fully formulated lubricating oil composition (oil of lubricating viscosity plus all additives) will be no greater than 12, such as no greater than 10, preferably no greater than 8.
  • Fully formulated lubricating oil compositions of the present invention preferably have a sulfated ash (SASH)content of less than about 0.5 wt. %.
  • the most recent and stringent industry standard test for evaluating the ability of diesel engine oils to control soot-induced viscosity increase is conducted in a T-11, EGR-equipped diesel engine, and is commonly referred to as the "Mack T-11" test (ASTM designation number not yet assigned).
  • the Mack T-11 test determines the used oil soot load at which the difference between used oil KV-100 (kinematic viscosity at 100°C, reported in cSt.) and KV-100 of a sheared fresh oil sample exceeds 12. To pass, a lubricating oil composition must score at least 6 (6% soot load). Higher numbers indicate better results (more soot handling capability).
  • a comparison between the results achieved with the base lubricant and Comp. 1 demonstrates that increased nitrogen content improves Mack T-11 performance to a certain extent.
  • Testing of Comp. 2 shows that the use of a low molecular weight dispersant, at higher nitrogen content, causes a debit in Mack T-11 performance, as does the introduction of low molecular weight DPA (Comp. 3).
  • the combination of a high molecular weight dispersant and a small amount of an aminated, high molecular weight olefin copolymer provides an improvement in soot handling performance far greater than would be forecast based on compositional nitrogen content.
  • the Mack T-11 results demonstrate that compositions of the invention achieve Mack T-11 results exceeding those of compositions containing approximately double the amount of dispersant nitrogen (Comp 1), even in the presence the performance debit-causing low molecular weight DPA antioxidant.
  • Lubricating oil samples prepared with a Group I base oil and a base DI package identical but for the dispersant employed, were tested in a Haake Rheometer according to the above procedure, at a carbon black level of 4.76 wt. % and a shear rate of 0.45 sec -1 .
  • the samples all contained PIBSA-PAM-type dispersants of varying functionalities and molecular weight distributions; the amount of dispersant in each sample was adjusted to provide comparable dispersant nitrogen levels.
  • Dispersants having a MWD of 1.8 were based on HR-PIB while those having a MWD of 2.1 were derived from conventional PIB.
  • Viscosity (Pa.s E 1.8 0.050 0.00 5.02 F 1.8 0.050 0.27 7.35 G 2.1 0.050 0.00 4.00 H 2.1 0.050 0.13 6.30 I 1.8 0.025 0.00 6.06 J 1.8 0.025 0.27 7.19 K 2.1 0.025 0.00 7.42 L 2.1 0.025 0.13 9.02
  • compositions described as "comprising" a plurality of defined components are to be construed as including compositions formed by mixing the defined plurality of defined components.

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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)

Claims (10)

  1. Composition d'huile lubrifiante comprenant une quantité majeure d'au moins l'une d'une huile minérale de viscosité propre à la lubrification du Groupe I, du Groupe II, du Groupe III, ou un de leurs mélanges ; une quantité mineure d'un ou plusieurs polymères ayant un poids moléculaire entre 20 000 et 750 000, comprenant un copolymère éthylène-propylène greffé avec de l'anhydride maléique et dérivé avec une arylamine, le copolymère fournissant de 0,0003 à 0,008 % en poids d'azote à la composition d'huile lubrifiante ; et une quantité mineure d'au moins un dispersant polyalcénylsuccinimide qui est le produit de réaction d'un anhydride succinique substitué par un polyalcényle et d'une polyamine, et a un rapport de couplage de 0,65 à 1,25 ; au moins un des dispersants polyalcénylsuccinimide ayant un groupement polyalcényle avec un poids moléculaire moyen en nombre de 1 800 à 3 000, une distribution de poids moléculaires (Mp/Mn) de 1,5 à 2, et de 1,3 à 1,7 groupements anhydride succinique par groupement polyalcényle ; le dispersant contribuant à au moins 0,08 % en poids de l'azote dans la composition d'huile lubrifiante.
  2. Composition d'huile lubrifiante selon la revendication 1, dans laquelle la quantité totale des groupements diarylamine dans la composition d'huile lubrifiante est de 0,5 à 5 mmol/kg, et plus de 50 % desdits groupements diarylamine sont dérivés de molécules ayant un poids moléculaire moyen en nombre de plus de 5000.
  3. Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, qui comprend en outre de 6 à 50 mmol de tensioactif phénate par kilogramme d'huile lubrifiante finie.
  4. Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle ledit dispersant comprend de 1,3 à 1,6 groupements anhydride succinique par groupement de polyalcényle, et a une teneur en bore de moins de 20 ppm.
  5. Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, ayant une teneur en cendres sulfatées de moins de 0,5 % en poids.
  6. Composition d'huile lubrifiante selon la revendication 1, ayant une teneur en soufre de moins d'environ 0,3 % en poids, une teneur en cendres sulfatées de moins de 0,5 % en poids et une teneur en chlore de moins de 50 ppm, le dispersant étant exempt de chlore.
  7. Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle la molécule d'oléfine de haut poids moléculaire, fonctionnalisée, est dérivée d'un copolymère amorphe éthylène-propylène, ou d'un mélange d'un copolymère éthylène-propylène amorphe et semi-cristallin avec un SSI de 5 à 30, produit par le cisaillement et la fonctionnalisation simultanés des copolymères éthylène-propylène de poids moléculaire plus élevé, avec de l'anhydride maléique, dans une extrudeuse.
  8. Composition d'huile lubrifiante selon la revendication 7, dans laquelle ledit copolymère éthylène-propylène semi-cristallin a une structure conique et est produit dans un réacteur tubulaire.
  9. Procédé de fonctionnement d'un moteur diesel, lequel procédé comprend l'étape de lubrification dudit moteur avec une composition d'huile lubrifiante selon l'une quelconque des revendications précédentes.
  10. Procédé selon la revendication 9, dans lequel ledit moteur diesel est muni d'un système de recirculation de gaz d'échappement.
EP04256985.5A 2003-12-04 2004-11-11 Compositions d'huiles lubrifiantes Expired - Lifetime EP1538193B1 (fr)

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US20050124509A1 (en) 2005-06-09
CA2489035C (fr) 2015-02-24

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