EP2649167A1 - Schmiermittelzusammensetzung mit viskositätsindexverbesserer - Google Patents

Schmiermittelzusammensetzung mit viskositätsindexverbesserer

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Publication number
EP2649167A1
EP2649167A1 EP11799913.6A EP11799913A EP2649167A1 EP 2649167 A1 EP2649167 A1 EP 2649167A1 EP 11799913 A EP11799913 A EP 11799913A EP 2649167 A1 EP2649167 A1 EP 2649167A1
Authority
EP
European Patent Office
Prior art keywords
composition
mol
weight
polymer
oil
Prior art date
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.)
Granted
Application number
EP11799913.6A
Other languages
English (en)
French (fr)
Other versions
EP2649167B1 (de
Inventor
Chor Huang
David Price
Jack Kelley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Lubrizol Corp
Original Assignee
Lubrizol Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP2649167A1 publication Critical patent/EP2649167A1/de
Application granted granted Critical
Publication of EP2649167B1 publication Critical patent/EP2649167B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
    • 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
    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, 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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, 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
    • 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
    • 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
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    • 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
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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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
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/08—Amides
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
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    • 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—Overbasedsulfonic 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
    • 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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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/017—Specific gravity or density
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    • C10N2020/019—Shear stability
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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    • 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
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    • 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
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    • 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
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    • 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
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
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    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2040/251—Alcohol-fuelled engines
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    • C10N2040/252—Diesel engines
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    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
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    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
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    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines

Definitions

  • This invention relates to lubricant compositions containing viscosity index (VI) improvers. More particularly, this invention relates to lubricant compositions containing VI improvers in the form of polymers comprising structural units derived from ethylene, propylene and butylene.
  • VI viscosity index
  • Petroleum products typically exhibit large variations in viscosity with variations in temperature. However, for lubricating oil compositions used for automobiles and the like, it is preferable that the temperature dependence of the viscosity be small. In order to decrease the temperature dependence of viscosity, olefin copolymers have been added to lubricating oil compositions as VI improvers.
  • Ethylene-propylene copolymers have been used for many years as VI improvers in multigrade engine oil formulations. In most cases these VI improvers contain at least about 40% by weight ethylene. While these copolymers are effective VI improvers, they have the disadvantage of contributing to piston deposits and oil thickening when the oils are subjected to high temperature operations. This invention provides a solution to this problem.
  • This invention relates to lubricant compositions containing VI improvers that comprise polymers with structural units derived from ethylene, propylene, and butylene. These lubricant compositions, when used as engine oils, exhibit reduced levels of piston deposits and reduced levels of viscosity increase, as compared to conventional lubricant compositions, when the engine is operated under high temperature conditions.
  • This invention relates to a lubricant composition, comprising: an oil of lubricating viscosity; and a viscosity index improving amount of a polymer comprising from about 5 mol % to about 20 mol % structural units derived from ethylene, from about 50 mol% or 60 mol % to about 90 mol% structural units derived from propylene, and from about 5% to about 30 mol % structural units derived from butylene.
  • the lubricant composition further comprises a dispersant and a detergent comprising an overbased sulfonate wherein the sulfonate has a total base number in the range from about 250 to about 600.
  • hydrocarbyl and “hydrocarbon,” when referring to groups attached to the remainder of a molecule, refer to groups having a purely hydrocarbon or predominantly hydrocarbon character within the context of this invention. Such groups include the following:
  • Substituted hydrocarbon groups that is, groups containing non-hydrocarbon substituents which do not alter the predominantly hydrocarbon character of the group. Examples include hydroxy, nitro, cyano, alkoxy, acyl, etc.
  • Hetero groups that is, groups which, while predominantly hydrocarbon in character, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Examples include nitrogen, oxygen and sulfur.
  • oil-soluble refers to a material that is soluble in mineral oil to the extent of at least about 0.5 gram per liter at 25°C.
  • TBN refers to total base number. This is the amount of acid (perchloric or hydrochloric) needed to neutralize all or part of a material's basicity, expressed as milligrams of KOH per gram of sample. TBN is commonly reported without correcting for the amount of oil or other diluent that may be present in a material and is used in this manner in this document, unless otherwise specified.
  • TAN refers to total acid number. This is the amount of base (NaOH or KOH) needed to neutralize all or part of a material's acidity, expressed as milligrams of KOH per gram of sample.
  • the lubrication composition may be comprised of one or more base oils which may be present in a major amount.
  • the base oil may be present in an amount greater than about 60% by weight, or greater than about 70%, or greater than about 75% by weight of the lubricant composition.
  • the lubricant composition may have a viscosity of up to about 26.1 cSt at 100°C, or from about 5.6 to about 26.1 cSt at 100°C, or from about 6 to about 16.3 cSt at 100 C, or from about 6 to about 13 cSt at 100°C.
  • the lubricant composition may have an SAE Viscosity Grade of OW-20, OW-30, OW-40, OW-50, OW-60, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W-20, 10W-30, 10W-40, 10W-50, 15W-20, 15W-30, 15W-40, 15W-50 or 15W-60.
  • the oil of lubricating viscosity may be referred to as a base oil.
  • the base oil may be selected from any of the base oils in Groups l-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • API American Petroleum Institute
  • Group I >0.03 and/or ⁇ 90 80 to 120
  • PAO polyalphaolefins
  • the base oil may contain less than about 300 ppm sulfur and/or at least about 90% saturate content, determined by test procedure described in ASTM D2007.
  • the base oil may have a viscosity index of at least about 95, or at least about 1 15.
  • the base oil may have a viscosity index of at least about 120, and comprise one or more polyalphaolefins.
  • the base oil may have a viscosity index of up to about 130.
  • the oil of lubricating viscosity may comprise a Group II oil.
  • the oil or oils of lubricating viscosity within the lubricant composition may overall have the qualities of a Group II oil or, alternatively, a Group III oil, even though the overall base oil may be prepared by blending multiple oils of various Groups.
  • Groups I, II and III are mineral oil base stocks.
  • the base oil may comprise natural or synthetic lubricating oils and mixtures thereof. Mixture of mineral oil and synthetic oils, particularly polyalphaolefin oils and ester oils, may be used.
  • Natural oils may include animal oils and vegetable oils (e.g. castor oil, lard oil, and other vegetable acid esters) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Hydrotreated or hydrocracked oils may be included within the scope of useful oils.
  • animal oils and vegetable oils e.g. castor oil, lard oil, and other vegetable acid esters
  • mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Hydrotreated or hydrocracked oils may be included within the scope of useful oils.
  • Base oils derived from coal or shale may be useful.
  • Synthetic lubricating oils may include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins and mixtures thereof, alkylbenzenes, polyphenyl, (e.g., biphenyls, terphenyls, and alkylated polyphenyls), alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues thereof.
  • hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins and mixtures thereof, alkylbenzenes, polyphenyl, (e.g., biphenyls, terphenyls, and alkylated polyphenyls), alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivative
  • Alkylene oxide polymers and interpolymers and derivatives thereof, and those where terminal hydroxyl groups have been modified by, for example, esterification or etherification, may constitute other classes of known synthetic lubricating oils that can be used.
  • Another suitable class of synthetic lubricating oils that may be used comprises the esters of dicarboxylic acids and those made from about C5 to about C12 monocarboxylic acids and polyols or polyol ethers.
  • suitable synthetic lubricating oils may include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, silicon-based oils such as the poly-alkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils, and silicate oils.
  • Hydrotreated naphthenic oils may be used.
  • Synthetic oils may be used, such as those produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes.
  • the base oil may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid procedures.
  • Unrefined, refined and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove may be used.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Rerefined oils may be obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. The rerefined oils often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • the amount of oil in a fully formulated lubricant will typically be the amount remaining to equal 100 percent after the remaining additives are accounted for. Typically this may be from about 60 to about 99 percent by weight, or from about 70 to about 97 percent, or from about 80 to about 95 percent, or from about 85 to about 93 percent by weight.
  • the lubricant composition may be delivered as a concentrate, in which case the amount of oil is typically reduced and the concentrations of the other components are correspondingly increased. In such cases the amount of oil may be from about 30 to about 70 percent by weight, or from about 40 to about 60 percent by weight.
  • the lubricant composition contains a viscosity index improving amount of a polymer comprising structural units derived from ethylene, propylene and butylene.
  • the polymer may be prepared by polymerizing a mixture of monomers comprising ethylene, propylene and butylene. These polymers may be referred to as copolymers or terpolymers.
  • the polymer may comprise from about 5 mol % to about 20 mol %, or from about 5 mol % to about 10 mol % structural units derived from ethylene; from about 60 mol % to about 90 mol %, or from about 60 mol % to about 75 mol % structural units derived from propylene; and from about 5 mol % to about 30 mol %, or from about 15 mol % to about 30 mol % structural units derived from butylene.
  • the butylene may comprise any isomers or mixtures thereof, such as n-butylene, iso-butylene, or a mixture thereof.
  • the butylene may comprise butene-1 .
  • butylene may comprise butene-1 as well as butene-2 and butadiene.
  • the butylene may comprise a mixture of butene-1 and isobutylene wherein the weight ratio of butene-1 to isobutylene is about 1 :0.1 or less.
  • the butylene may comprise butene-1 and be free of or essentially free of isobutylene.
  • the polymer may have a number average molecular weight (as determined by gel permeation chromatography (GPC) using polystyrene as the calibration standard) in the range from about 10,000 to about 500,000; or from about 30,000 to about 400,000 or from about 50,000 to about 350,000, or from about 150,000 to about 250,000.
  • the molecular weight distribution, Mw/Mn, (as determined by GPC using polystyrene as the calibration standard, where Mw is the weight average molecular weight, and Mn is the number average molecular weight) of the polymer may be about 4 or less, or about 3 or less, or about 2.5 or less, or in the range from about 2 to about 4, or in the range from about 2 to about 3, or in the range from about 2 to about 2.5.
  • the method for producing the polymer may comprise polymerizing propylene, ethylene, and butylene (e.g., butene-1 ) in the presence of known catalysts which can conduct stereoregular polymerization of olefins into isotactic configuration or syndiotactic configuration (for example, a catalyst whose principle components are a titanium component in solid form and an organic metal compound or a metallocene catalyst in which a metallocene compound is used as a component of the catalyst).
  • a production method which uses a metallocene catalyst which can conduct stereoregular polymerization in isotactic configuration may be used in order to obtain a lubricant composition having excellent fuel efficiency at a high temperature.
  • metallocene catalysts examples include those described in International Publication WO 2004/106430, International Publication WO 2005/019283, International Publication WO 2006/025540 and International Publication WO 2004/087775.
  • the metallocene compounds may include diphenylmethylene(3-tert-butyl-5- ethylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride, diphenyl- methylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)- zirconium dichloride, dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)- (fluorenyl )zirconium dichloride, and the like.
  • the polymer may be present on a weight basis in the lubricant composition at a concentration in the range from about 0.001 % to about 2%, or in the range from about 0.003% to about 1 .5%, or in the range from about 0.005 to about 1 %, or in the range from about 0.01 % to about 0.75%.
  • the polymer may present at a concentration in the range from about 0.5% to about 1 %, or from about 0.6 to about 0.8% by weight. In other embodiments it may be present at about 0.3 to about 5 percent by weight or about 0.5 to about 2 percent by weight.
  • the polymer may be provided in a concentrate.
  • the concentrate may comprise a diluent oil, and from about 0.5% to about 30% by weight polymer, or from about 1 % to about 15% polymer, or from about 5% to about 15% by weight polymer.
  • the following example shows the preparation of an ethylene-propylene- butylene polymer that may be used as a viscosity index improver in the lubricant composition.
  • TMAO-341 TOSO FINECHEM CORPORATION
  • NL normal liters, that is, liters at 1 atmosphere and 0 °C)
  • NL normal liters, that is, liters at 1 atmosphere and 0 °C
  • the vapor phase is forcibly circulated using a gas blower which is separately equipped, the vapor phase is cooled by a heat exchanger, and thereby polymerization heat is removed.
  • the polymerization product that is produced is a hexane solution comprising an ethylene/propylene/butene-1 polymer. This solution is withdrawn at a rate of 7.5 kg/hr in terms of the ethylene/propylene/butene-1 copolymer through an outlet equipped at the bottom of the polymerization reactor so that the average of solution amount in the polymerization reactor is kept at 100L.
  • the resultant polymerization solution is poured into methanol to precipitate the ethylene/propylene/butene-1 polymer.
  • the ethylene/propylene/butene-1 polymer is dried under reduced pressure at 130°C for 24 hours.
  • the polymer contains 8.7 mol % structural units derived from ethylene, 68 mol % structural units derived from propylene, and 23.3 mol % structural units derived by butene-1 .
  • the polymer has a density of 865 kg/m 3 , a melting point of 47°C, a Mw of 220,000, and a Mw/Mn of 2.2, as determined by GPC using polystyrene as the calibration standard.
  • the lubricant composition may contain one or more overbased metal- containing detergents.
  • Overbased materials otherwise referred to as overbased or superbased salts may be single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased materials may be prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, such as carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a calcium chloride, acetic acid, phenol or alcohol.
  • the acidic organic material may have a sufficient number of carbon atoms to provide a degree of solubility in oil. The amount of excess metal is commonly expressed in terms of metal ratio.
  • metal ratio is the ratio of the total equivalents of the metal to the equiva- lents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 3.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • metal ratio is also explained in standard textbook entitled “Chemistry and Technology of Lubricants,” Second Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 1997.
  • the metal of the overbased metal-containing detergent may be zinc, sodium, calcium, barium, magnesium, or a mixture of two or more thereof.
  • the metal may be sodium, calcium, or magnesium or mixtures thereof; in one embodiment the metal may be a mixture of sodium and calcium.
  • the overbased metal-containing detergent may be selected from non- sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
  • the lubricant composition may be free from or substantially free from phenol-based detergent or detergents. "Substantially free from” means, in this context, less than 10 weight percent, or less than 5 or 1 or 0.1 weight percent of the detergent or detergents may be phenol-based.
  • the overbased detergent may be borated with a borating agent such as boric acid.
  • the overbased metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate-salicylates, sulfonate-phenates, sulfonate- salicylates, sulfonates-phenates-salicylates, as described; for example, in US Patents 6,429,178; 6,429,179; 6,153,565; and 6,281 ,179.
  • phenate-salicylates e.g. phenate-salicylates, sulfonate-phenates, sulfonate- salicylates, sulfonates-phenates-salicylates, as described; for example, in US Patents 6,429,178; 6,429,179; 6,153,565; and 6,281 ,179.
  • hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing corresponding amounts of phenate and sulfonate soaps, respectively.
  • the overbased metal-containing detergent may comprise zinc, sodium, calcium or magnesium salts of a phenate, sulfur containing phenate, sulfonate, salixarate or salicylate.
  • Overbased salixarates, phenates and salicylates may have a total base number (ASTM D3896) in the range from about 180 to about 450 TBN.
  • Overbased sulfonates may have a total base number in the range from about 250 to about 600, or in the range from about 300 to about 500.
  • Overbased detergents are known in the art.
  • the sulfonate detergent may be a predominantly linear alkylbenzene or alkyltoluene sulfonate detergent having a metal ratio of at least about 8 as is described in paragraphs [0026] to [0037] of U.S. Patent Publication 2005/065045.
  • the linear alkyl group may be attached to the benzene or toluene at any location along the linear alkyl chain, such as at the 2, 3, or 4 position.
  • the linear alkylbenzene sulfonate detergent may be useful for improving fuel economy.
  • the overbased metal-containing detergent may be a calcium or magnesium overbased detergent.
  • the lubricant composition may comprise an overbased calcium sulfonate, an overbased calcium phenate, or a mixture thereof.
  • the overbased detergent may comprise a calcium sulfonate with a metal ratio of at least about 3.5, for example, in the range from about 3.5 to about 40, or in the range from about 5 to about 25, or in the range from about 7 to about 20.
  • the lubricant composition may further comprise a low overbased detergent (metal ratio of less than about 3.5, for example, in the range from about 0 to about 3.5, or in the range from about 0.5 to about 3.0, or in the range from about 1 to about 2.5, or in the range from about 1 .5 to about 2) or a neutral detergent.
  • a low overbased detergent metal ratio of less than about 3.5, for example, in the range from about 0 to about 3.5, or in the range from about 0.5 to about 3.0, or in the range from about 1 to about 2.5, or in the range from about 1 .5 to about 2
  • a neutral detergent metal ratio of less than about 3.5, for example, in the range from about 0 to about 3.5, or in the range from about 0.5 to about 3.0, or in the range from about 1 to about 2.5, or in the range from about 1 .5 to about 2
  • the overbased metal-containing detergent may be present in the lubricant composition at a concentration in the range from about 0.05% by weight to about 5% by weight of the lubricant composition.
  • the overbased detergent may be present at a concentration in the range from about 0.1 %, about 0.3%, or about 0.5% up to about 3.2%, or about 1 .7%, or about 0.9% by weight of the lubricant composition.
  • the overbased detergent may be present in an amount suitable to provide a TBN (total base number) in the range from about 1 to about 10 to the lubricant composition.
  • the overbased detergent may be present in amount which provides a TBN in the range from about 1 .5 up to about 3, or up to about 5, or up to about 7, to the lubricant composition.
  • the overbased detergent may provide at least 3 TBN to the lubricant composition, such as 3 to 7 or 4 to 6 TBN.
  • Metal-containing detergents in addition to TBN, may also provide ash to the lubricant composition.
  • Sulfated ash ASulfated ash (ASTM D874) is another parameter often used to characterize overbased detergents and lubricant compositions.
  • the lubricant composition may have sulfated ash levels of about 0.3 to about 1 .2% by weight, or from about 0.3 to about 1 .0% or from about 0.5 to about 1 .0%, or greater than about 0.6%. In other embodiments (e.g., for marine diesel cylinder lubricants) the ash level may be from about 1 to about 15%, or from about 2 to about 12% by weight, or from about 4 to about 10%.
  • the overbased detergent may account for about 50% to about 100% of the sulfated ash, or at least about 70% of the ash, or at least about 80% of the ash, or 100% of the ash.
  • the overbased detergent may provide for no more than about 95% of the sulfated ash, or no more than about 98% of the sulfated ash.
  • the lubricant composition may be a marine diesel cylinder lubricant
  • Lubricants of this type may be characterized by high TBN levels delivered primarily by metal containing overbased detergents.
  • the lubricant composition may have a TBN of at least about 10, or at least about 20, e.g., 10-100, 20-100, 30-100, 40-80, 30-75, or 40-70.
  • Most of the basicity of the MDCL composition may be contributed by the detergent component, although typically a relatively small amount (e.g., less than about 5%) of the TBN may be contributed by other species such as nitrogen-containing dispersants.
  • the lubricant composition may comprise other performance additives.
  • These may include one or more metal deactivators, supplemental viscosity modifiers, supplemental detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, mixtures of two or more thereof.
  • Antioxidants may include sulfurized olefins, diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), hydroxyl thioethers, or mixtures thereof.
  • the antioxidant may be present at a concentration in the range from about 0 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 0.5 wt % to about 5 wt %, or about 0.5 wt % to about 3 wt % of the lubricant composition.
  • the diarylamine or alkylated diarylamine may be a phenyl alpha- naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In one embodiment the diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • the hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert- butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4- butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant may be an ester, such as the ester available under the tradename IrganoxTM L-135 from Ciba. Such materials may be represented by the general formula
  • R 3 is a hydrocarbyl group such as an alkyl group containing, e.g., 1 to about 18, or 2 to about 12, or 2 to about 8, or 2 to about 6 carbon atoms; and t- alkyl can be t-butyl.
  • ester-containing hindered phenol antioxidants that may be used may be found in US Patent 6,559,105.
  • molybdenum dithiocarbamates which may be used as an antioxidant include commercial materials sold under trade names such as Vanlube 822TM and MolyvanTM A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-LubeTM S-100, S-165, S-525 and S-600 from Asahi Denka Kogyo K. K, and mixtures thereof.
  • the lubricant composition may further include one or more supplemental viscosity modifiers. These may include hydrogenated styrene-butadiene rubbers, ethylene-propylene copolymers, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, poly(alkyl styrenes), polyolefins, esters of maleic anhydride-olefin copolymers (such as those described in International Application WO 2010/014655), esters of maleic anhydride-styrene copolymers, or mixtures or two or more thereof.
  • supplemental viscosity modifiers may include hydrogenated styrene-butadiene rubbers, ethylene-propylene copolymers, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, poly(alkyl styrenes), polyo
  • the dispersant viscosity modifier may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalized with an amine; or esterified styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication WO2006/015130 or U.S. Patents 4,863,623; 6,107,257; 6,107,258; and 6,1 17,825. The dispersant viscosity modifier may include those described in U.S.
  • the dispersant viscosity modifier may be present at a concentration of up to about 15 wt %, or up to about 10 wt %, or in the range from about 0.05 wt % to about 5 wt %, or from about 0.2 wt % to about 2 wt % of the lubricant composition.
  • the lubricant composition may further include one or more dispersants.
  • the dispersant may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or mixtures thereof.
  • the dispersant may be present as a single dispersant, or it may be present as a mixture of two or more (e.g., three) different dispersants, wherein at least one may be a succinimide dispersant.
  • the succinimide dispersant may be derived from one or more aliphatic polyamines.
  • the aliphatic polyamine may be an aliphatic polyamine such as ethylenepolyamine (i.e., a poly(ethyleneamine)), a propylenepolyamine, a butylenepolyamine, or a mixture of two or more thereof.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene- pentamine, pentaethylenehexamine, polyamine still bottoms, or a mixture of two or more thereof.
  • the succinimide dispersant may be derived from an aromatic amine, aromatic polyamine, or mixture thereof.
  • the aromatic amine may have one or more aromatic moieties linked by a hydrocarbylene group and/or a heteroatom such as 4-amino diphenylamine.
  • the aromatic amine may be a nitro-substituted aromatic amine. Examples of nitro-substituted aromatic amines may include 2- nitroaniline, 3-nitroaniline, and 4-nitroaniline. 3-nitroaniline may be particularly useful. Other aromatic amines may be present along with the nitroaniline. Condensation products with nitroaniline and optionally also with Disperse Orange 3 (that is, 4-(4-nitrophenylazo)aniline) are disclosed in U.S. Patent Publication 2006/0025316.
  • the dispersant may comprise a polymer functionalized with an amine, e.g., a succinimide dispersant.
  • the amine may be an amine having at least 2, or at least 3, or at least 4 aromatic groups, for instance, from about 4 to about 10, or from about 4 to about 8, or from about 4 to about 6 aromatic groups, and at least one primary or secondary amino group or, alternatively, at least one secondary amino group.
  • the amine may comprise both a primary and at least one secondary amino group.
  • the amine may comprise at least about 4 aromatic groups and at least 2 of any combination of secondary or tertiary amino groups.
  • An example of an amine having 2 aromatic groups is N-phenyl-p- phenylenediamine.
  • An example of an amine having at least 3 or 4 aromatic groups may be represented by Formula (1 ):
  • R 1 may be hydrogen or a C-i -5 alkyl group (typically hydrogen);
  • R 2 may be hydrogen or a C-i -5 alkyl group (typically hydrogen);
  • U may be an aliphatic, alicyclic or aromatic group (when U is aliphatic, the aliphatic group may be a linear or branched alkylene group containing 1 to about 5, or 1 to about 2 carbon atoms); and w may be from 1 to about 10, or 1 to about 4, or 1 to 2 (typically 1 ).
  • U may be an alkylene group containing 1 to about 5 carbon atoms.
  • the amine may also be represented by Formula (1 a)
  • each variable U, R 1 , and R 2 are the same as described above and w is 0 to about 9, or 0 to about 3, or 0 to about 1 (typically 0).
  • the dispersant may be a polyolefin succinic acid ester, amide, or ester- amide.
  • a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof.
  • a polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (such as a polyamine, typically diethylenetriamine, polyamine still bottoms, tetraethylenepentamine (TEPA), and the like).
  • the dispersant may be an N-substituted long chain alkenyl succinimide.
  • An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide, that is, a polyisobutene substituted succinimide dispersant.
  • the polyisobutylene from which polyisobutylene succinic anhydride is derived has a number average molecular weight of from about 350 to about 5000, or from about 550 to about 3000 or from about 750 to about 2500.
  • Succinimide dispersants and their preparation are disclosed, for instance in US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281 , 3,351 ,552, 3,381 ,022, 3,433,744, 3,444,170, 3,467,668, 3,501 ,405, 3,542,680, 3,576,743, 3,632,51 1 , 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP Patent Application 0 355 895 A.
  • the dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents such as boric acid
  • boron compounds such as boric acid
  • urea such as urea
  • thiourea dimercaptothiadiazoles
  • carbon disulfide aldehydes
  • ketones carboxylic acids such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • the dispersant may be present in the lubricant composition at a concentration in the range from about 0.01 wt % to about 20 wt %, or from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 6 wt %, or from about 1 to about 3 wt % of the lubricating composition.
  • the dispersant contains basic nitrogen atoms, such basicity may be measured as TBN of the dispersant.
  • TBN of a useful succinimide dispersant may be about 10 to about 30 on an oil-free (corrected) basis, which would correspond to about 5 to about 15 if measured on a dispersant sample containing 50% oil.
  • the viscosity index improving amount of the polymer (that is, the amount of the VI polymer) is about 0.5 to about 2 percent by weight, the amount of the dispersant is about 0.01 to about 20 percent by weight, and the amount of the overbased sulfonate is about 0.05 to about 5 percent by weight.
  • the friction modifier may be selected from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of a long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides.
  • fatty alkyl or fatty in relation to friction modifiers means a carbon chain having from about 10 to about 22 carbon atoms, typically a straight carbon chain. Alternatively, mono-branched alkyl groups may be used in place of the fatty alkyl groups.
  • Typical mono-branched alkyl groups may include beta-branched groups such as 2-ethylhexyl, 2-propylheptyl, and the like.
  • the friction modifier may be present in the lubricant composition at a concentration in the range from 0 wt % to about 6 wt %, or about 0.01 wt % to about 4 wt %, or from about 0.05 wt % to about 2 wt %, or from about 0.1 wt % to about 2 wt % of the lubricant composition.
  • friction modifiers may include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyalkyl and polyhydroxyalkyl fatty amines including tertiary hydroxyalkyl fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines;
  • Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphat.es, molybdenum dithiocarbamates, and monoesters of a polyol and an aliphatic carboxylic acid derived or derivable from sunflower oil or soybean oil.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester, diester, (tri)glyceride, or a mixture of two or more thereof.
  • the lubricant composition may optionally further include at least one antiwear agent.
  • suitable antiwear agents may include tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphat.es), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
  • the antiwear agent may, in one embodiment, include a tartrate, or tartrimide as disclosed in International Publication WO 2006/04441 1 or Canadian Patent CA 1 183 125.
  • the tartrate or tartrimide may contain alkyl group(s), where the sum of carbon atoms on the alkyl groups is at least about 8.
  • the oil soluble titanium compound may be a titanium (IV) alkoxide.
  • the titanium alkoxide may be formed from a monohydric alcohol, a polyol or mixtures thereof.
  • the monohydric alkoxides may contain from 2 to about 16 carbon atoms, or from 3 to about 10 carbon atoms.
  • the titanium alkoxide may be titanium (IV) isopropoxide.
  • the titanium alkoxide may be titanium (IV) 2-ethylhexoxide.
  • the titanium compound may comprise the alkoxide of a vicinal 1 ,2-diol or polyol.
  • the 1 ,2-vicinal diol may comprise a fatty acid mono-ester of glycerol, such as oleic acid esters.
  • the oil soluble titanium compound may be a titanium carboxylate.
  • the titanium carboxylate may be derived from a titanium alkoxide and a carboxylic acid selected from the group consisting of a non-linear mono-carboxylic acid and a carboxylic acid having more than about 22 up to about 25 carbon atoms.
  • titan ium/carboxylic acid products may include titanium reaction products with acids selected from the group comprising caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.
  • acids selected from the group comprising caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.
  • EP agents may include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-1 ,3,4- thiadiazole, or oligomers thereof, organic sulfides and polysulfides such as dibenzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl pho
  • Foam inhibitors that may be used in the lubricant composition may include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate, and optionally also vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • Pour point depressants that may be used in the lubricant composition may include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • Demulsifiers that may be used may include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures of two or more thereof.
  • Metal deactivators may include derivatives of benzotriazoles (typically tolyltriazole), 1 ,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2- alkyldithio-benzothiazoles.
  • the metal deactivators may also be described as corrosion inhibitors.
  • Seal swell agents that may be used may include sulfolene derivatives such as Exxon Necton-37TM (FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
  • the lubricant composition may be used to lubricate a mechanical device, by supplying the lubricant as described herein to the device.
  • the device may be an internal combustion engine such as a gasoline-fired or diesel-fired automobile engine, a heavy duty diesel engine, a marine diesel engine, or a stationary gas engine.
  • Such engines may be sump lubricated, and the lubricant may be provided to the sump from whence it may lubricate the moving parts of the engine.
  • the lubricant may be supplied from a separate source, not a part of a sump.
  • the internal combustion engine may be a diesel fueled engine (typically a heavy duty diesel engine), a gasoline fueled engine, a natural gas fueled engine, a mixed gasoline/alcohol fueled engine, or a hydrogen fueled internal combustion engine.
  • the internal combustion engine may be a diesel fueled engine or a gasoline fueled engine.
  • the internal combustion engine may be a heavy duty diesel engine.
  • the internal combustion engine may be a 2-stroke or 4-stroke engine.
  • Suitable internal combustion engines may include marine diesel engines (which may comprise a cylinder which is lubricated with said lubricant), aviation piston engines, low-load diesel engines, and automobile and truck engines.
  • the marine diesel engine may be lubricated with a marine diesel cylinder lubricant (typically in a 2-stroke engine), a system oil (typically in a 2-stroke engine), or a crankcase lubricant (typically in a 4-stroke engine).
  • One class of internal combustion engines is direct injected combustion engines wherein the fuel is injected directly into the cylinder.
  • Specific examples of direct injection may include wall guided and spray guided direct injection engines.
  • the lubricant composition may be used to lubricate a gasoline direct injection engine.
  • the lubricant composition may be suitable for use as any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash content.
  • the sulfur content of the lubricant composition when used as an engine oil may be about 1 wt % or less, or about 0.8 wt % or less, or about 0.5 wt % or less, or about 0.3 wt % or less.
  • the sulfur content may be in the range of about 0.001 wt % to about 0.5 wt %, or about 0.01 wt % to about 0.3 wt %.
  • the phosphorus content may be about 0.2 wt % or less, or about 0.12 wt % or less, or about 0.1 wt % or less, or about 0.085 wt % or less, or about 0.08 wt % or less, or about 0.06 wt % or less, or about 0.055 wt % or less, or about 0.05 wt % or less.
  • the phosphorus content may be from about 0.04 wt % to about 0.12 wt %.
  • the phosphorus content may be from about 100 ppm to about 1000 ppm, or about 200 ppm to about 600 ppm.
  • the total sulfated ash content may be about 0.3 wt % to 1 .2 wt %, or about 0.5 wt % to about 1 .1 wt % of the lubricant composition.
  • the sulfated ash content may be about 0.5 wt % to 1 .1 wt % of the lubricant composition.
  • the lubricant composition may be characterized by a chlorine content of up to about 100 ppm, or up to about 50 ppm, or up to about 10 ppm.
  • the lubricant composition may be an engine oil, wherein the lubricant composition may be characterized as having at least one of (i) a sulfur content of about 0.5 wt % or less, (ii) a phosphorus content of about 0.12 wt % or less, and (iii) a sulfated ash content of about 0.5 wt % to about 1 .1 wt % of the lubricant composition.
  • the lubricant composition may be a marine diesel cylinder lubricant, which may be used to lubricate a marine diesel cylinder.
  • the marine diesel cylinder may be in a 2-stroke marine diesel engine.
  • Marine diesel cylinder lubricants are typically used for one pass and are consumed, rather than being retained in a sump. These lubricants may require a high detergent level, imparting high levels of basicity as measured by TBN to the lubricant, typically resulting in TBN levels of about 20 or greater, such as about 30 or greater, or about 40 or greater, or about 50 or greater, or about 70 or greater, and typically up to about 80, or up to about 100, or up to about 300.
  • the lubricant composition may be used in a method of operating an internal combustion engine wherein piston deposit merit ratings are increased and viscosity increase is reduced.
  • the disclosed technology provides a method of reducing levels of piston deposits in an internal combustion engine, comprising lubricating the engine with a lubricant composition as described herein.
  • the disclosed technology provides The use of a viscosity index improving amount of a polymer comprising from about 5 mol % to about 20 mol % structural units derived from ethylene, from about 50 mol % to about 90 mol% structural units derived from propylene, and from about 5% to about 30 mol % structural units derived from butylene, in a lubricant composition further comprising an oil of lubricating viscosity, a dispersant; and a detergent comprising an overbased sulfonate wherein the sulfonate has a total base number in the range from about 250 to about 600, to reduce the level of piston deposits in an engine lubricated by said lubricant composition.
  • each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material (that is, on an active chemical basis), unless otherwise indicated, e.g., unless an amount of oil is indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.

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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)
EP11799913.6A 2010-12-10 2011-12-06 Schmiermittelzusammensetzung mit viskositätsindexverbesserer Active EP2649167B1 (de)

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US42176410P 2010-12-10 2010-12-10
PCT/US2011/063425 WO2012078572A1 (en) 2010-12-10 2011-12-06 Lubricant composition containing viscosity index improver

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JP (1) JP5897030B2 (de)
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CA2820583C (en) 2018-10-30
CN103354832B (zh) 2015-11-25
EP2649167B1 (de) 2016-03-09
KR101815338B1 (ko) 2018-01-30
WO2012078572A1 (en) 2012-06-14
CA2820583A1 (en) 2012-06-14
KR20130130003A (ko) 2013-11-29
CN103354832A (zh) 2013-10-16
JP5897030B2 (ja) 2016-03-30
US20140005086A1 (en) 2014-01-02
JP2013544948A (ja) 2013-12-19
SG190994A1 (en) 2013-07-31

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