EP2467456A1 - Composition lubrifiante contenant un agent anti-usure - Google Patents

Composition lubrifiante contenant un agent anti-usure

Info

Publication number
EP2467456A1
EP2467456A1 EP10747108A EP10747108A EP2467456A1 EP 2467456 A1 EP2467456 A1 EP 2467456A1 EP 10747108 A EP10747108 A EP 10747108A EP 10747108 A EP10747108 A EP 10747108A EP 2467456 A1 EP2467456 A1 EP 2467456A1
Authority
EP
European Patent Office
Prior art keywords
lubricating composition
phenate
detergent
aluminium
lubricating
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
EP10747108A
Other languages
German (de)
English (en)
Other versions
EP2467456B1 (fr
EP2467456B2 (fr
Inventor
Mark C. Davies
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.)
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
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Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP2467456A1 publication Critical patent/EP2467456A1/fr
Publication of EP2467456B1 publication Critical patent/EP2467456B1/fr
Application granted granted Critical
Publication of EP2467456B2 publication Critical patent/EP2467456B2/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10M2207/027—Neutral 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
    • C10M2207/02—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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • 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
    • C10M2215/28—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
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10M2223/043—Ammonium or amine 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/45—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
    • 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]
    • 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
    • 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
    • C10N2040/251—Alcohol-fuelled 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle 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
    • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur

Definitions

  • the invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium- alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent.
  • the phenate disclosed herein may further provide antiwear performance on the aluminium-alloy surface.
  • lubricating oils It is well known for lubricating oils to contain a number of surface active additives (including antiwear agents, dispersants, or detergents) used to protect internal combustion engines from corrosion, wear, soot deposits and acid build up. Often, such surface active additives can have harmful effects on engine component wear (in both iron and aluminium based components), bearing corrosion or fuel economy.
  • a common antiwear additive for engine lubricating oils is zinc dialkyldithiophosphate (ZDDP). It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces. ZDDP may also have a detrimental impact on fuel economy and efficiency and copper corrosion. Consequently, engine lubricants may also contain a friction modifier to obviate the detrimental impact of ZDDP on fuel economy and corrosion inhibitors to obviate the detrimental impact of ZDDP on copper corrosion. Other additives may also increase lead corrosion.
  • non-ferric engine components are based on aluminium-alloy, silicates, oxides, or other ceramic materials.
  • Antiwear additives such as ZDDP are believed to result in poorer engine wear performance in aluminium-alloy based engine compared with ferric based engines.
  • EP 624 044 Al discloses a method of lubricating an aluminium alloy surface with a lubricating composition containing an effective friction reducing amount of an oil soluble tri-nuclear organo-molybdenum compound.
  • WO2008/144701 discloses lubricating an aluminium- alloy surface by supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an ashless antiwear agent.
  • the examples disclosed therein also indicate 1.5 wt % of detergent. However, there is no specific disclosure of the type of detergent utilised.
  • the present invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal (including lithium, sodium, calcium, magnesium, or barium) phenate detergent.
  • a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal (including lithium, sodium, calcium, magnesium, or barium) phenate detergent.
  • the phenate detergent may be a calcium sulphurised-phenate, in particular an overbased calcium sulphurised-phenate.
  • the present invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising (a) an oil of lubricating viscosity, (b) an overbased alkali or alkaline earth metal (including lithium, sodium, calcium, magnesium, or barium, typically calcium) phenate (typically a sulphurised-phenate) detergent having a TBN of 200 to 400 (or
  • a neutral phenate typically a non-sulphur containing calcium phenate
  • a neutral phenate typically a non-sulphur containing calcium phenate
  • the non-sulphur containing calcium phenate may include detergents described in European Patent applications EP 1 680 491 A, or EP 1 778 824 A.
  • the present invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • the invention provides a method of controlling wear of an aluminium-alloy surface in an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • the invention provides for the use of the lubricating composition disclosed herein to mitigate wear on an aluminium alloy surface of an internal combustion engine.
  • the invention provides for the use of an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised- phenate) as an antiwear agent for an aluminium alloy surface of an internal combustion engine.
  • the invention provides a method of lubricating an internal combustion engine as disclosed herein, wherein the aluminium alloy is an eutectic or hyper-eutectic aluminium alloy (such as those derived from aluminium silicates, aluminium oxides, or other ceramic materials).
  • the aluminium alloy is an eutectic or hyper-eutectic aluminium alloy (such as those derived from aluminium silicates, aluminium oxides, or other ceramic materials).
  • the invention provides a method of lubricating an internal combustion engine as disclosed herein, wherein the internal combustion engine has part or all of a cylinder bore, cylinder block, or piston ring composed of an aluminium alloy, or aluminium composite.
  • the present invention provides a lubricating composition and a method for lubricating an engine as disclosed above.
  • the alkali or alkaline earth metal phenate detergent may be described as an overbased material.
  • Overbased materials otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterised by an amount of excess metal beyond that which would be necessary for neutralisation according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the amount of excess metal is commonly expressed in terms of substrate to metal ratio.
  • substrate to metal ratio alternatively expressed as the metal to substrate ratio, or simply “metal ratio” is the ratio of the total equivalents of the metal to the equivalents of the substrate.
  • metal ratio is provided in "Chemistry and Technology of Lubricants", Second Edition, Edited by R. M. Mortier and S. T. Orszulik, pages 85 and 86, 1997.
  • the overbased alkali or alkaline earth metal phenate detergent may have a metal ratio of 0.8 to 10, or 1 to 10, or 3 to 9, or 4 to 8, or 5 to 7.
  • the alkali or alkaline earth metal phenate detergent may have a total base number (TBN) 50 to 400, or 200 to 350, or 220 to 300. In one embodiment the alkali or alkaline earth metal phenate detergent may have a TBN of about 255.
  • TBN total base number
  • a more detailed description of the alkali or alkaline earth metal phenate detergent is described in for example, US Patent 6,551,965, or European Patent applications EP 1 903 093 A and EP 0 601 721 A.
  • the alkali or alkaline earth metal phenate detergent additive may be derived from a hydrocarbyl-substituted phenol, wherein the hydrocarbyl-substituted phenol may be present in range from 10 wt % to 70 wt %, or 25 wt % to 65 wt %, or
  • the additive When the additive is added to a lubricant the overall percentage reduces due to diluent effect of all the base oil and presence of other additives in the overall lubricating composition.
  • the alkali or alkaline earth metal phenate detergent may be derived from a hydrocarbyl-substituted phenol, wherein the alkaline earth metal phenate detergent delivers 0.75 wt % to 2 wt %, or 0.9 wt % to 1.75 wt %, or 1 wt % to 1.5 wt % of hydrocarbyl-substituted phenol to the lubricating composition.
  • the hydrocarbyl- substituted phenol content (this includes the phenol and anions thereof) delivered by the alkali or alkaline earth metal phenate detergent may vary from 0.75 wt % to 2 wt %, or 0.9 wt % to 1.75 wt %, or 1 wt % to 1.5 wt % of the lubricating composition.
  • the alkali or alkaline earth metal phenate detergent hydrocarbyl- substituted phenol content and sulphated ash may vary.
  • the hydrocarbyl-substituted phenol content delivered by the phenate may be 0.9 wt % to 1.75 wt %; and the sulphated ash content may be at least 0.4 wt % to 1.3 wt % of the lubricating composition.
  • the hydrocarbyl-substituted phenol content delivered by the phenate may be 0.9 wt % to 1.75 wt %; and the sulphated ash content may be at least 0.4 wt % to 1.2 wt % of the lubricating composition.
  • the hydrocarbyl-substituted phenol content delivered by the phenate may be 1 wt % or higher to 1.5 wt %; and the sulphated ash content may be at least 0.6 wt % to 1.1 wt % of the lubricating composition.
  • Each hydrocarbyl group of hydrocarbyl-substituted phenol may contain on average 6 or more, 8 or more, or 10 or more carbon atoms.
  • the maximum number of carbon atoms per hydrocarbyl group may be up to 300, or up to 100, or up to 70, or up to 50, or up to 20.
  • each hydrocarbyl group may 8 to 20, or 10 to 12 carbon atoms (typically each hydrocarbyl group may be dodecyl).
  • the amount of sulphated ash delivered by the overbased alkali or alkaline earth metal phenate detergent may be 0.4 wt % to 1.2 wt %, or 0.6 wt % to 1.1 wt % of the lubricating composition.
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content.
  • the sulphur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of
  • the phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the sulphated ash content of the lubricating composition may be at least 0.3 wt%, or at least 0.4 wt %, at least 0.6 wt % up to 2 wt %, or 1.5 wt %, or 1.3 wt %, or 1.1 wt % of the lubricating composition.
  • the sulphated ash content may in different embodiments range from 0.3 wt % to 2 wt %, or 0.4 wt % to 1.5 wt %, or 0.6 wt % to 1.3 wt %, or 0.6 wt % to 1.1 wt % of the lubricating composition.
  • the lubricating composition may be characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.06 wt % or less, and (iii) a sulphated ash content of 1.3 wt % or less.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydro finishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704, paragraphs [0054] to [0056].
  • a more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of WO2008/147704.
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.
  • oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • Oils of lubricating viscosity may also be defined as specified in April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3.
  • oil of lubricating viscosity may be an API Group I, or Group II, or Group III, or Group IV oil. In one embodiment the oil of lubricating viscosity may be an API Group II or Group III oil.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the compound of the invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubricant, the ratio of the of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
  • the composition optionally comprises other performance additives.
  • the other performance additives include at least one of metal deactivators, viscosity modifiers, detergents (in addition to the phenate previously described as part of the invention), friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
  • fully-formulated lubricating oil will contain one or more of these performance additives.
  • the lubricating composition further includes other additives.
  • the invention provides a lubricating composition further comprising at least one of a dispersant, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, a detergent (in addition to the phenate previously described as part of the invention), or mixtures thereof.
  • the dispersant of the present invention may be a succinimide dispersant, or mixtures thereof.
  • the dispersant may be present as a single dispersant.
  • the dispersant may be present in a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.
  • the succinimide dispersant may be derived from an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the dispersant may be a N-substituted long chain alkenyl succinimide.
  • N-substituted long chain alkenyl succinimide examples include polyisobutylene succinimide.
  • polyisobutylene succinimide typically the polyisobutylene from which the polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.
  • Succinimide dispersants and their preparation are disclosed, for instance in US Patents 3,172,892,
  • the dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents include boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt % of the lubricating composition.
  • the lubricating composition of the invention further comprises a dispersant viscosity modifier.
  • the dispersant viscosity modifier may be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt % of the lubricating composition.
  • the dispersant viscosity modifier may include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalised with an amine, or 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 6,117,825. In one embodiment the dispersant viscosity modifier may include those described in
  • fatty has at least 6 or at least 8 to 30, or 20 carbon atoms.
  • the friction modifier may be selected from the group consisting of fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids.
  • the friction modifier may be present at 0 wt % to 6 wt %, or 0.05 wt % to 4 wt %, or 0.1 wt % to 2 wt % of the lubricating composition
  • the invention provides a lubricating composition which further includes a zinc dialkyldithiophosphate, or mixtures thereof.
  • Zinc dialkyldithiophosphates are known in the art.
  • the zinc dialkyldithiophosphate may be present at 0 wt % to 5 wt %, or 0.1 wt % to 3 wt %, or 0.5 wt % to 2 wt % of the lubricating composition.
  • the invention provides a lubricating composition further comprising a molybdenum compound.
  • the molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof.
  • the molybdenum compound may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • the invention provides a lubricating composition further comprising a neutral or an overbased detergent in addition to the phenate previously described as part of the invention.
  • the neutral or overbased detergent may be selected from the group consisting of sulphonates, salixarates, salicylates, saligenins and mixtures thereof.
  • the neutral or overbased detergent may be a sodium, calcium or magnesium salt of the sulphonates, salixarates and salicylates.
  • Neutral detergents may have a TBN of less than 200, or typically less than 170.
  • a "neutral" or “slightly overbased" sulphonate detergent may have a TBN of 0 to 100 or 20 to 100 (such as 80 or 85).
  • the lubricating composition may contain 0 wt % to 5 wt % or 0.5 to 3 wt % of a neutral sulphonate detergent (typically calcium sulphonate) with a TBN of 80 or 85.
  • the lubricating composition may contain 0 wt % to 3 wt %, or 0.5 to 2 wt % of a calcium phenate detergent with a TBN of 155. (A neutral phenate detergent, i.e., not overbased, will typically still exhibit a measurable TBN.)
  • Overbased phenates and salicylates typically have a total base number of 200 to 450 TBN. Overbased sulphonates typically have a total base number of 250 to 600, or 300 to 500 (typically 300 or 400).
  • Overbased detergents are known in the art. In one embodiment the sulphonate detergent may be a predominantly linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 to 40 as is described in paragraphs [0026] to [0037] of US Patent Application
  • the predominantly linear alkylbenzene sulphonate detergent may be particularly useful for assisting in improving fuel economy.
  • the total amount of neutral and overbased detergent in addition to the claimed phenate may be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt % of the lubricating composition (including amounts of diluent oil known to be conventionally associated with detergents. This may for instance be 30 to 50 wt % of the ranges quoted).
  • the lubricating composition includes an antioxidant, or mixtures thereof.
  • the antioxidant may be present at 0 wt % to 15 wt 5, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt % of the lubricating composition.
  • Antioxidants include sulphurised olefins, alkylated diphenylamines
  • the hindered phenol antioxidant often contains 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 and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
  • Suitable friction modifiers include 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; or fatty di- alkyl tartramides.
  • Friction modifiers may also encompass materials such as sulphurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be selected from the group consisting of fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
  • the fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides may be the same or different to the amide, ester or imide derivative of a hydroxy- carboxylic acid described above.
  • the friction modifier may be a fatty acid ester.
  • the fatty acid ester may be a mono-ester and in another embodiment the fatty acid ester may be a (tri)glyceride.
  • corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319, published as WO2006/047486, octylamine octanoate, or condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
  • the corrosion inhibitors include the Synalox® corrosion inhibitor.
  • the Synalox® corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.
  • the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
  • the product brochure is entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding
  • Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1 ,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides may be useful.
  • benzotriazoles typically tolyltriazole
  • dimercaptothiadiazole derivatives 1 ,2,4-triazoles
  • benzimidazoles 2-alkyldithiobenzimi
  • Foam inhibitors that may be useful in the compositions of the invention include copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • pour point depressants that may be useful in the compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • the lubricating composition may in addition to the detergent of the invention have a composition further containing additive in ranges described in the following table:
  • Ranges quoted above are on an oil free basis i.e., amount of active ingredient with diluent oil factored out.
  • the lubricating composition may be utilised in an internal combustion engine.
  • the internal combustion engine may or may not have an Exhaust Gas Recirculation system.
  • the internal combustion engine may be fitted with an emission control system or a turbocharger.
  • Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
  • the internal combustion engine may be a diesel fuelled engine (typically a heavy duty diesel engine), a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine.
  • the internal combustion engine may be a diesel fuelled engine and in another embodiment a gasoline fuelled engine.
  • the internal combustion engine may be a 2-stroke or 4-stroke engine. Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines.
  • Comparative Lubricant Examples 1 to 5 are prepared by blending a mixture of succinimide dispersants (total amount of succinimide dispersants 8.3 wt % including 40 wt % diluent oil), 3 wt % of a dispersant viscosity modifier commercially sold as Hitec®5777 (including diluent oil), 4 wt % of a mixture of antioxidants (including amine and phenolic antioxidants), and 1.2 wt % of glycerol monooleate friction modifier.
  • CEl to CE5 contain overbased detergent as is described in the table below. Also included is the charactisation data for each lubricant indicating sulphated ash content and total base number (TBN mg KOH/g).
  • Amount of each detergent quoted includes conventional amounts of diluent oil (typically ranging from 30 to 50 wt %).
  • Comparative Lubricant Examples 6 to 7 are prepared by blending a mixture of succinimide dispersants (total amount of succinimide dispersants 7.9 wt % including 40 wt % diluent oil), a mixture of antioxidants (including amine and phenolic antioxidants), and 0.57 wt % of a zinc dialkyldithiophosphate.
  • CE6 and CE7 contain 2 wt % (including diluent oil) and 2.7 wt % (including diluent oil) of overbased calcium sulphonate respectively.
  • Invention Lubricant Examples 1 and 2 are similar to CE6 and CE7, except EXl contains 1.9 wt % (including 39 wt % diluent oil) and 2.75 wt % (including 39 wt % diluent oil) of overbased calcium sulphurised- phenate respectively in place of overbased calcium sulphonate.
  • CE6, CE7, EXl and EX2 are characterised as follows:
  • HFRR temperature high frequency reciprocating rig
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.

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Abstract

L’invention concerne un procédé de lubrification d’une surface d’alliage d’aluminium d’un moteur à combustion interne comprenant l’application sur la surface d’alliage d’aluminium d’une composition lubrifiante comprenant une huile de viscosité lubrifiante et un détergent de phénate de métal alcalin ou de métal alcalino-terreux. Le phénate selon l'invention peut présenter en outre des performances anti-usure sur la surface d’alliage d’aluminium.
EP10747108.8A 2009-08-18 2010-08-10 Procede de lubrification Active EP2467456B2 (fr)

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104099158B (zh) * 2013-04-15 2017-10-27 广州泛海节能科技有限公司 网状晶格纳米球润滑油改善剂
US10494584B2 (en) * 2013-09-19 2019-12-03 The Lubrizol Corporation Lubricant compositions for direct injection engines
CN104263461B (zh) * 2014-10-09 2016-07-06 王严绪 一种陶瓷合金复合功能耦合剂及其制备方法

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
DE1271877B (de) 1963-04-23 1968-07-04 Lubrizol Corp Schmieroel
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
USRE26433E (en) 1963-12-11 1968-08-06 Amide and imide derivatives of metal salts of substituted succinic acids
GB1052380A (fr) 1964-09-08
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
DE1595234A1 (de) 1965-04-27 1970-03-05 Roehm & Haas Gmbh Verfahren zur Herstellung oligomerer bzw. polymerer Amine
US3340281A (en) 1965-06-14 1967-09-05 Standard Oil Co Method for producing lubricating oil additives
US3433744A (en) 1966-11-03 1969-03-18 Lubrizol Corp Reaction product of phosphosulfurized hydrocarbon and alkylene polycarboxylic acid or acid derivatives and lubricating oil containing the same
US3501405A (en) 1967-08-11 1970-03-17 Rohm & Haas Lubricating and fuel compositions comprising copolymers of n-substituted formamide-containing unsaturated esters
US3576743A (en) 1969-04-11 1971-04-27 Lubrizol Corp Lubricant and fuel additives and process for making the additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
GB8818711D0 (en) 1988-08-05 1988-09-07 Shell Int Research Lubricating oil dispersants
US6117825A (en) 1992-05-07 2000-09-12 Ethyl Corporation Polyisobutylene succinimide and ethylene-propylene succinimide synergistic additives for lubricating oils compositions
DE69327515T2 (de) 1992-12-07 2000-06-21 Ethyl Petroleum Additives, Inc. Verfahren zur Herstellung von überbasischen Phenolaten
US6165235A (en) 1997-08-26 2000-12-26 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US6107258A (en) 1997-10-15 2000-08-22 Ethyl Corporation Functionalized olefin copolymer additives
US6107257A (en) 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
US6174842B1 (en) * 1999-03-30 2001-01-16 Ethyl Corporation Lubricants containing molybdenum compounds, phenates and diarylamines
US6551965B2 (en) 2000-02-14 2003-04-22 Chevron Oronite Company Llc Marine diesel engine lubricating oil composition having improved high temperature performance
US6559105B2 (en) 2000-04-03 2003-05-06 The Lubrizol Corporation Lubricant compositions containing ester-substituted hindered phenol antioxidants
DE60203639T2 (de) 2001-11-05 2006-01-19 The Lubrizol Corp., Wickliffe Schmiermittelzusammensetzung mit verbesserter Brennstoffersparnis
US7238650B2 (en) 2002-06-27 2007-07-03 The Lubrizol Corporation Low-chlorine, polyolefin-substituted, with amine reacted, alpha-beta unsaturated carboxylic compounds
US6969198B2 (en) * 2002-11-06 2005-11-29 Nissan Motor Co., Ltd. Low-friction sliding mechanism
US20040224858A1 (en) * 2003-05-06 2004-11-11 Ethyl Corporation Low sulfur, low ash, and low phosphorus lubricant additive package using overbased calcium phenate
US6921512B2 (en) * 2003-06-24 2005-07-26 General Motors Corporation Aluminum alloy for engine blocks
EP1680491B1 (fr) 2003-10-30 2012-12-26 The Lubrizol Corporation Compositions lubrifiantes contenant des sulfonates et des phenates
SG128780A1 (en) * 2004-07-09 2007-02-26 Shell Int Research Lubricating oil composition
JP5158939B2 (ja) 2004-07-29 2013-03-06 ザ ルブリゾル コーポレイション 潤滑組成物
US20060025315A1 (en) * 2004-07-30 2006-02-02 Rebecca Oldfield Method for lubricating surfaces
CA2574969C (fr) 2004-07-30 2013-05-07 The Lubrizol Corporation Modifiants de viscosite de dispersant contenant des amines aromatiques
EP1624044A1 (fr) 2004-07-30 2006-02-08 Infineum International Limited Méthode pour lubrifier des surfaces
EP1824950A1 (fr) 2004-10-25 2007-08-29 The Lubrizol Corporation Inhibition de la corrosion
CN101522935B (zh) * 2006-08-01 2012-09-26 昭和电工株式会社 铝合金成形品的制造方法、铝合金成形品以及生产系统
EP1903093B1 (fr) 2006-09-19 2017-12-20 Infineum International Limited Composition d'huile de lubrification
US20080090741A1 (en) * 2006-10-16 2008-04-17 Lam William Y Lubricating oils with enhanced piston deposit control capability
IN2009CN02056A (fr) * 2006-10-17 2015-08-07 Idemitsu Kosan Co
JP2008180218A (ja) * 2006-12-28 2008-08-07 Yamaha Motor Co Ltd 内燃機関用部品およびその製造方法
US20080294468A1 (en) 2007-05-21 2008-11-27 J. Key Corporation Process for automating and simplifying commercial insurance transactions
CA2688098C (fr) 2007-05-24 2016-04-19 The Lubrizol Corporation Composition lubrifiante contenant un agent anti-usure
CA2688094C (fr) * 2007-05-24 2017-07-04 The Lubrizol Corporation Procede de lubrification d'une surface composite de silicate d'aluminium avec un lubrifiant comprenant un agent anti-usure depourvu de soufre, de phosphore, sans cendre
JP4458496B2 (ja) * 2008-04-16 2010-04-28 株式会社豊田中央研究所 筒内噴射式内燃機関、筒内噴射式内燃機関用ピストン、筒内噴射式内燃機関用ピストンの製造方法
JP5394021B2 (ja) * 2008-08-06 2014-01-22 アイシン精機株式会社 アルミニウム合金ピストン部材およびその製造方法
JP4706736B2 (ja) * 2008-08-12 2011-06-22 Ｔｄｋ株式会社 コイル用ボビン、コイル巻線、及びコイル部品
US20130165357A1 (en) * 2011-12-22 2013-06-27 Exxonmobil Research & Engineering Company Lubricant compositions for SI-AL alloy surfaces and methods for using

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011022245A1 *

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IN2012DN01625A (fr) 2015-06-05
BR112012003694A2 (pt) 2016-03-29

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