EP1262538A2 - Additifs anti-usure et antioxydants pour compositions d'huile lubrifiantes - Google Patents

Additifs anti-usure et antioxydants pour compositions d'huile lubrifiantes Download PDF

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Publication number
EP1262538A2
EP1262538A2 EP02076732A EP02076732A EP1262538A2 EP 1262538 A2 EP1262538 A2 EP 1262538A2 EP 02076732 A EP02076732 A EP 02076732A EP 02076732 A EP02076732 A EP 02076732A EP 1262538 A2 EP1262538 A2 EP 1262538A2
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EP
European Patent Office
Prior art keywords
mass
metal salt
composition
oil composition
detergent
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
EP02076732A
Other languages
German (de)
English (en)
Other versions
EP1262538B1 (fr
EP1262538A3 (fr
Inventor
Christopher John Locke
Mark Stevens
Peter Wrench
Rebecca Claro Castle
Stephen Arrowsmith
Jane Rachel Galsworthy
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.)
Infineum International Ltd
Original Assignee
Infineum International Ltd
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
Priority claimed from EP01201752A external-priority patent/EP1256619A1/fr
Priority claimed from GB0128734A external-priority patent/GB0128734D0/en
Application filed by Infineum International Ltd filed Critical Infineum International Ltd
Priority to EP02076732.3A priority Critical patent/EP1262538B1/fr
Priority to EP04256980A priority patent/EP1518920A1/fr
Publication of EP1262538A2 publication Critical patent/EP1262538A2/fr
Publication of EP1262538A3 publication Critical patent/EP1262538A3/fr
Application granted granted Critical
Publication of EP1262538B1 publication Critical patent/EP1262538B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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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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    • C10M2215/00—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
    • C10M2215/066—Arylene diamines
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    • C10M2215/28—Amides; Imides
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/088—Neutral salts
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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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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    • 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
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/18—Anti-foaming property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—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
    • C10N2030/52—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
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur
    • 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
    • C10N2060/12—Chemical after-treatment of the constituents of the lubricating composition by phosphorus or a compound containing phosphorus, e.g. PxSy
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention concerns the use of a defined detergent composition in a lubricating oil composition for reducing wear in an engine. It also relates to a lubricating oil composition for use in an internal combustion engine, preferably a heavy duty diesel engine, and a method for the preparation thereof.
  • Catalytic converters in the exhaust systems have been used to reduce the emission of pollutants.
  • Such converters generally use a combination of catalytic metals, such as platinum or variations thereof and metal oxides, and are installed in the exhaust streams, e.g. the exhaust pipes of automobiles to convert the toxic gases to non-toxic gases.
  • Phosphorus components such as the decomposition products of the zinc dithiophosphate, are believed to poison the catalyst in these converters.
  • sulfur components poison the catalysts, for example those used in reduction of nitrogen oxides.
  • phosphorus-, sulfur- and molybdenum-containing compounds as anti-wear and/or anti-oxidant additives.
  • a particular detergent composition provides anti-wear benefit to lubricating oil compositions having a low phosphorus content, and optionally a low sulfur content, preferably to lubricating oil compositions which have both low phosphorus and low sulfur contents.
  • the present invention provides the use, in a minor amount, of a detergent composition comprising one or more metal detergents which comprises metal salts of organic acids, wherein the detergent composition comprises more than 50 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition, in a lubricating oil composition for reducing wear in an engine, wherein the amount of phosphorus and sulfur in the oil composition is less than 0.09 mass % and at most 0.5 mass % respectively, based on the mass of the oil composition.
  • Another particular detergent composition provides oxidation resistance to lubricating oil compositions having a low phosphorus content, and optionally a low sulfur content, preferably to lubricating oil compositions which have both low phosphorus and low sulfur contents
  • the present invention provides the use, in a minor amount, of a detergent composition comprising one or more metal detergents which comprises metal salts of organic acids, wherein the detergent composition comprises more than 50 mole %, based on the moles of the metal salts of organic acids in the detergent composition, of:
  • a lubricating oil composition for improving the oxidation resistance or control of the lubricating oil composition, wherein the amount of phosphorus and sulfur in the oil composition is less than 0.09 mass % and at most 0.5 mass % respectively, based on the mass of the oil composition.
  • the present invention provides an SAE 5WX or SAE 0WX lubricating oil composition comprising:
  • the present invention provides a lubricating oil composition comprising:
  • the present invention provides a lubricating oil composition comprising:
  • the present invention provides a lubricating oil composition comprising:
  • the present invention provides an additive composition, for preparing a lubricating oil composition according to any one of the third to sixth aspect, having less than 0.6 mass % of phosphorus and, preferably, at most 2.5 mass % of sulfur, based on the mass of the additive composition, said additive composition comprising:
  • the present invention provides a method of lubricating an internal combustion engine, preferably a heavy duty diesel engine, comprising supplying to the engine the lubricating oil composition according to any one of the third to sixth aspect.
  • the present invention provides a method of preparing a lubricating oil composition of any one of the third to sixth aspect comprising admixing components (A), (B) and (C) as defined in the corresponding third to sixth aspect or admixing an additive composition of the seventh aspect and an oil of lubricating viscosity as defined in the corresponding third to sixth aspect.
  • the present invention provides the use of an oil composition according to any one of the third to sixth aspect for reducing wear in an engine.
  • the amount of phosphorus, in respect of each aspect, in the lubricating oil composition, independently of the amount of sulfur, is less than 0.08, less than 0.07 or less than 0.06, more preferably at most 0.05, at most 0.04 or at most 0.03, such as in the range from 0.001 to 0.03, for example at most 0.02 or at most 0.01, mass %, based on the mass of the oil composition.
  • the phosphorus content is zero in the lubricating oil composition.
  • the amount of sulfur, in respect of each aspect, in the lubricating oil composition, independently of the amount of phosphorus, is preferably at most 0.45, or at most 0.4, or at most 0.35, or at most 0.3, or at most 0.25, especially at most 0.2 or at most 0.15, such as in the range from 0.001 to 0.1 or 0.005 to 0.05, mass %, based on the mass of the oil composition.
  • the sulfur content is zero in the lubricating oil composition
  • the amount of phosphorus and sulfur is derived from an anti-wear additive, such as a zinc dithiophosphate.
  • the amount of chlorine in the lubricating oil composition is at most 100, preferably at most 50, such as at most 30, more preferably at most 20, especially at most 10, for example from 0 to 5, ppm, based on the mass of the oil composition. It is advantagesous to reduce the amount of chlorine so as to decrease the production of dioxins.
  • the amount of phosphorus and sulfur in the lubricating oil composition is preferably derived from both (B) and (C); more preferably the amount is derived from (A), (B) and (C).
  • the lubricating oil composition is in the form of an SAE 5WX or SAE OWX lubricating oil composition, wherein X represents any one of 20, 30, 40 and 50. Preferably, X represents 20 or 30.
  • the amount of nitrogen is preferably at least 0.01 or at least 0.02, more preferably at least 0.05, such as at least 0.055, advantageously at least 0.06, especially at least 0.065, such as at least 0.1, mass %, based on the mass of the oil composition.
  • the amount of nitrogen is preferably at most 0.3, such as at most 0.25, or at most 0.2, or at most 0.15, mass %, based on the mass of the oil composition.
  • the amount of nitrogen is derived from a dispersant additive, such as a polyisobutenyl succinimide.
  • the amount of anti-oxidant additive is at least 0.1, preferably at least 0.5, especially at least 1.0, most preferably at most 5.0, mass %, based on the mass of the oil composition.
  • the lubricating oil composition does not comprise one or more of a co-additive (C) selected from a phosphorus-containing compound, a sulfur-containing compound and a molybdenum-containing compound.
  • a co-additive (C) selected from a phosphorus-containing compound, a sulfur-containing compound and a molybdenum-containing compound.
  • the lubricating oil composition does not comprise a phosphorus-containing and/or a molybdenum-containing compound, such as a zinc dithiodiphosphate and/or a molybdenum dithiocarbamate.
  • the lubricating oil compositions of the present invention are preferably crankcase lubricating oil compositions suitable for lubricating an internal combustion engine, preferably a passenger car engine or a heavy duty diesel engine.
  • Examples of passenger car engines are light duty diesel engines and gasoline engines.
  • the heavy duty trucking market has come to adopt the diesel engine as its preferred power source due to both its excellent longevity and its economy of operation.
  • Specialized lubricants have been developed to meet the more stringent performance requirements of heavy duty diesel engines.
  • API American Petroleum Institute
  • API Association des Constructeur Europeén d'Automobile
  • JASO Japanese Standards Organisation
  • a heavy duty lubricating oil composition of the present invention preferably satisfies at least the performance requirements of heavy duty diesel engine lubricants, such as at least the API CG-4; preferably at least the API CH-4; especially at least the API CI-4.
  • the lubricating oil composition of the invention independently of meeting the API performance requirements, preferably satisfies at least the ACEA E2-96; more preferably at least the ACEA E3-96; especially at least ACEA E4-99; advantageously at least the ACEA E5-99.
  • the lubricating oil composition of the invention, independently of meeting the API and ACEA performance requirements preferably satisfies the JASO DH-1 or Global DHD-1.
  • the lubricating oil composition preferably satisfies at least the performance requirements of API SH; more preferably at least the API SJ; especially at least the API SL.
  • the lubricating oil composition of the invention independently of meeting the API performance requirements, preferably satisfies at least the ACEA A2-96 (issue 2), more preferably at least the ACEA A3-98, especially at least the ACEA A1-98, for gasoline engines; and at least ACEA B2-98, more preferably at least the ACEA B1-98, such as at least the ACEA B3-98, especially at least the ACEA B4-98, for light duty diesel engines.
  • the defined metal detergent composition according to the first aspect has been found to exhibit anti-wear properties in lubricating oil compositions having a low phosphorus content, and optionally a low sulfur content.
  • the amount of phosphorus or sulfur in such an oil composition corresponds to the amount of phosphorus and sulfur disclosed above.
  • the anti-wear benefit is expected in the valve trains, journal bearing, and piston rings or liner; especially in the valve trains.
  • the present invention provides a lubricating oil composition according to the third aspect, but where the detergent composition comprises more than 50 mole %, based on the moles of the metal salts of organic acids in the detergent composition, of (B1) a metal salt of an aromatic carboxylic acid, and (C1) is a dispersant additive.
  • the oil composition gives less than 2, preferably less than 1.5, especially less than 1, advantageously less than 0.9 or 0.8 or 0.7 or 0.6, such as in the range from 0 or 0.1 or 0.2 or 0.3 or 0.4 to 0.5, mass % of sulfated ash, according to method ASTM D874.
  • Heavy duty diesel engines according to the present invention are preferably used in land-based vehicles, more preferably large road vehicles, such as large trucks.
  • the road vehicles typically have a weight greater than 12 tonnes.
  • the engines used in such vehicles tend to have a total displacement of at least 6.5, preferably at least 8, more preferably at least 10, such as at least 15, litres; engines having a total displacement of 12 to 20 litres are preferred.
  • engines having a total displacement greater than 24 litres are not considered land-based vehicles.
  • the engines according to the present invention also have a displacement per cylinder of at least 1.0 or at least 1.5, such as at least 1.75, preferably at least 2, litres per cylinder.
  • heavy duty diesel engines in road vehicles have a displacement per cylinder of at most 3.5, such as at most 3.0; preferably at most 2.5, litres per cylinder.
  • the terms 'total displacement' and 'displacement per cylinder' are known to those skilled in the art of internal combustion engines (see “Diesel Engine Reference Book", edited by B. Challen and R. Baranescu, second edition, 1999, published by SAE International). Briefly, the term 'displacement' corresponds to the volume of the cylinder in the engine as determined by the piston movement and consequently the 'total displacement' is the total volume dependent on the number of cylinders; and the term 'displacement per cylinder' is the ratio of the total displacement to the number of cylinders in the engine.
  • the present invention provides a combination of a heavy duty diesel engine, preferably in a land-based vehicle, which engine has a total displacement of at least 6.5 litres and a displacement per cylinder of at least 1.0 litre per cylinder and a lubricating oil composition as defined in any one of the third to sixth aspect.
  • the lubricating oil can be a synthetic or mineral oil of lubricating viscosity selected from the group consisting of Group I, II, III, IV or V basestocks and mixtures of thereof.
  • Basestocks may be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
  • Group IV basestocks i.e. polyalphaolefins (PAO)
  • PAO polyalphaolefins
  • Group IV basestocks include hydrogenated oligomers of an alpha-olefin, the most important methods of oligomerization being free radical processes, Ziegler catalysis, cationic, and Friedel-Crafts catalysis.
  • Group V basestocks in the form of esters are preferred and also tend to be commercially available.
  • examples include polyol esters such as pentaerythritol esters, trimethylolpropane esters and neopentylglycol esters; diesters; C 36 dimer acid esters; trimellitate esters, i.e., 1, 2, 4-benzene tricarboxylates; and phthalate esters, i.e., 1,2 - benzene dicarboxylates.
  • the acids from which the esters are made are preferably monocarboxylic acids of the formula RCO 2 H where R represents a branched, linear or mixed alkyl group. Such acids may, for example, contain 6 to 18 carbon atoms.
  • the lubricating oil is selected from any one of Group I to V basestocks, provided the selected basestock contains at most 0.5, such as at most 0.1 or at most 0.05, mass % of sulfur.
  • Group II, III, IV or V basestock or any two or more mixtures thereof, or mixtures of a Group IV basestock with 5 to 95, preferably 10 to 90, such as 20 to 85, mass %, of Group I, II, III or V basestock, provided the sulfur content is at most 0.5, such as at most 0.1 or at most 0.05, mass %.
  • a Group IV basestock and a Group V basestock in the form of an ester are considered synthetic basestocks.
  • the oil of lubricating viscosity comprises a synthetic basestock.
  • the oil of lubricating viscosity comprises at least one basestock selected from a Group IV basestock and a Group V basestock in the form of an ester.
  • the oil of lubricating viscosity consists essentially of:
  • test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for
  • a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of organic acids, also known as surfactants herein.
  • a detergent comprises a polar head, i.e. the metal salt of the organic acid, with a long hydrophobic tail for oil solubility. Therefore, the organic acids typically have one or more functional groups, such as OH or COOH or SO 3 H; and a hydrocarbyl substituent.
  • organic acids include sulfonic acids, phenols and sulfurised derivatives thereof, and carboxylic acids including aromatic carboxylic acids.
  • a metal detergent composition comprising more than 50 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition, provides a wear benefit, such as the ability to minimise the wear in an engine, to lubricating oil compositions having a low phosphorus content, and optionally a low sulfur content, preferably to lubricating oil compositions having low phosphorus and low sulfur contents.
  • the proportion of the metal salt of an aromatic carboxylic acid is at least 60 or at least 70, more preferably at least 80 or at least 90, mole %, based on the moles of the metal salts of organic acids in the detergent composition.
  • the detergent composition comprises 100 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition, that is the detergent composition comprises only aromatic carboxylic acids as the organic acids.
  • a metal detergent composition comprising more than 50 mole %, based on the moles of the metal salts of organic acids in the detergent composition, of:
  • the proportion of the metal salt selected from (I), (II) and (III) is preferably at least 60 or at least 70, more preferably at least 80 or at least 90, mole %, based on the moles of the metal salts of organic acids in the detergent composition.
  • the detergent composition comprises 100 mole % of a metal salt of both a metal salt of an aromatic carboxylic acid and a metal salt of a phenol, based on the moles of the metal salts of organic acids in the detergent composition, that is the detergent composition comprises only aromatic carboxylic acids and phenols as the organic acids.
  • a metal salt of an aromatic carboxylic acid and a metal salt of a phenol are present in the detergent composition, more of the metal salt of a phenol than the metal salt of an aromatic carboxylic acid is present, based on moles.
  • a detergent composition having only metal salts of phenols provides better oxidation resistance to a lubricating oil composition compared with detergent compositions having metal salts of aromatic carboxylic acids and/or metal salts of other organic acids, for example, sulfonic acids.
  • a detergent composition contains a metal salt of an aromatic carboxylic acid in an amount of more than 50 mole %, based on the moles of the organic acids in the detergent composition.
  • the aromatic moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen.
  • the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example benzene is a preferred moiety.
  • the aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.
  • the carboxylic moiety may be attached directly or indirectly to the aromatic moiety.
  • the carboxylic acid group is attached directly to a carbon atom on the aromatic moiety, such as a carbon atom on the benzene ring.
  • the aromatic moiety also contains a second functional group, such as a hydroxy group or a sulfonate group, which can be attached directly or indirectly to a carbon atom on the aromatic moiety.
  • a second functional group such as a hydroxy group or a sulfonate group
  • an aromatic carboxylic acids are salicylic acids and sulfurised derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof.
  • Salicylic acids are typically prepared by carboxylation, for example, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained, normally in a diluent, in admixture with uncarboxylated phenol.
  • Preferred substituents in oil-soluble salicylic acids are alkyl substituents.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil-solubility.
  • Phenols may be non-sulfurized or, preferably, sulfurized.
  • phenol as used herein includes phenols containing more than one hydroxyl group (for example, alkyl catechols) or fused aromatic rings (for example, alkyl naphthols) and phenols which have been modified by chemical reaction, for example, alkylene-bridged phenols and Mannich base-condensed phenols; and saligenin-type phenols (produced by the reaction of a phenol and an aldehyde under basic conditions).
  • Preferred phenols are of the formula
  • R represents a hydrocarbyl group and y represents 1 to 4. Where y is greater than 1, the hydrocarbyl groups may be the same or different.
  • the phenols are frequently used in sulfurized form. Details of sulfurization processes are known to those skilled in the art, for example, see US-A-4,228,022 and US-A-4,309,293.
  • hydrocarbyl groups represented by R are advantageously alkyl groups, which advantageously contain 5 to 100, preferably 5 to 40, especially 9 to 12, carbon atoms, the average number of carbon atoms in all of the R groups being at least about 9 in order to ensure adequate solubility in oil.
  • Preferred alkyl groups are nonyl (e.g. tripropylene) groups or dodecyl (e.g. tetrapropylene) groups.
  • phenol as used herein includes phenols which have been modified by chemical reaction with, for example, an aldehyde, and Mannich base-condensed phenols.
  • Aldehydes with which phenols may be modified include, for example, formaldehyde, propionaldehyde and butyraldehyde.
  • the preferred aldehyde is formaldehyde.
  • Aldehyde-modified phenols suitable for use in accordance with the present invention are described in, for example, US-A-5 259 967.
  • Mannich base-condensed phenols are prepared by the reaction of a phenol, an aldehyde and an amine. Examples of suitable Mannich base-condensed phenols are described in GB-A-2 121 432.
  • the phenols may include substituents other than those mentioned above.
  • substituents are methoxy groups and halogen atoms.
  • a preferred phenol is a sulfurised derivative thereof.
  • the detergent composition can comprise, in minor amounts, metal salts of organic acids other than aromatic carboxylic acids and phenols, such as sulfonic acids and carboxylic acids.
  • Sulfonic acids are typically obtained by sulfonation of hydrocarbyl-substituted, especially alkyl-substituted, aromatic hydrocarbons, for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • the alkylaryl sulfonic acids usually contain from about 22 to about 100 or more carbon atoms.
  • the sulfonic acids may be substituted by more than one alkyl group on the aromatic moiety, for example they may be dialkylaryl sulfonic acids.
  • the sulfonic acid has a number average molecular weight of 350 or greater, more preferably 400 or greater, especially 500 or greater, such as 600 or greater. Number average molecular weight may be determined by ASTM D3712.
  • Carboxylic acids include mono- and dicarboxylic acids.
  • Preferred monocarboxylic acids are those containing 8 to 30, especially 8 to 24, carbon atoms. (Where this specification indicates the number of carbon atoms in a carboxylic acid, the carbon atom(s) in the carboxylic group(s) is/are included in that number).
  • Examples of monocarboxylic acids are iso-octanoic acid, stearic acid, oleic acid, palmitic acid and behenic acid.
  • Iso-octanoic acid may, if desired, be used in the form of the mixture of C8 acid isomers sold by Exxon Chemical under the trade name "Cekanoic".
  • Suitable acids are those with tertiary substitution at the ⁇ -carbon atom and dicarboxylic acids with 2 or more carbon atoms separating the carboxylic groups. Further, dicarboxylic acids with more than 35 carbon atoms, for example, 36 to 100 carbon atoms, are also suitable. Unsaturated carboxylic acids can be sulfurized.
  • the metal detergent may be neutral or overbased, such terms are known in the art.
  • the detergents can have a Total Base Number (TBN) in the range of 15 or 60 to 600, preferably 100 to 450, more preferably 160 to 400. TBN is measured according to ASTM D-2896.
  • the detergents of the present invention may be salts of one type of organic acid or salts of more than one type of organic acids, for example hybrid complex detergents.
  • the detergent comprises metal salts of one type of organic acid.
  • a hybrid complex detergent is a detergent in which the basic material within the detergent is stabilised by metal salts of more than one type of organic acid. It will be appreciated by one skilled in the art that a single type of organic acid may contain a mixture of organic acids of the same type. For example, a sulfonic acid may contain a mixture of sulfonic acids of varying molecular weights. Such an organic acid composition is considered as one type. Thus, complex detergents are distinguished from mixtures of two or more separate, optionally overbased, detergents, an example of such a mixture being one of an overbased calcium salicylate detergent with an overbased calcium phenate detergent.
  • hybrid complex detergents examples include calcium phenate-salicylate-sulfonate detergent, calcium phenate-sulfonate detergent and calcium phenate-salicylate detergent.
  • EP-A-0 750 659 describes a calcium salicylate phenate complex made by carboxylating a calcium phenate and then sulfurising and overbasing the mixture of calcium salicylate and calcium phenate. Such complexes may be referred to as "phenalates"
  • Preferred complex detergents are salicylate-based detergents, for example, a calcium phenate-salicylate detergent and "phenalates”.
  • a preferred detergent contains metal salts of more than one type of organic acid (i.e. a hybrid complex detergent). Therefore, the detergent can contain, for example, a metal, preferably calcium, salt of a salicylic acid and/or a metal, preferably calcium, salt of a phenol, and a metal salt of another of organic acid, for example, a sulfonic acid.
  • the proportion of any one type of organic acid to another is not critical, provided the detergent composition comprises the defined proportion of the appropriate metal salt(s) as defined in the appropriate aspect of the present invention.
  • the detergent composition may also comprise an ashless detergent, i.e. a non-metal containing detergent.
  • the detergent composition comprises at least one overbased metal detergent, irrespective of whether the detergent contains metal salts of one type of organic acid or metal salts of more than one type of organic acid.
  • a preferred overbased metal detergent comprises a metal salt of an aromatic carboxylic acid, preferably a metal salt of a salicylic acid; or a metal salt of a phenol, preferably a metal salt of a sulfurised alkyl phenol; or both a metal salt of an aromatic carboxylic acid and a metal salt of a phenol.
  • Group 1 and Group 2 metals are preferred as metals in the detergents, more preferably calcium and magnesium, especially calcium.
  • Detergent compositions comprising, preferably consisting essentially of, at least one calcium salicylate-based detergent, preferably at least one overbased calcium salicylate-based detergent, have been found to particularly effective in providing anti-wear benefits, provided the proportion of the metal salt of an aromatic carboxylic acid, in this instance the metal salt of the salicylic acid, is satisfied. Therefore, detergent compositions comprising only calcium salicylate-based detergents, whether neutral or overbased, would be advantageous.
  • the calcium salicylate-based detergent may contain one or more metal, preferably calcium, salts of organic acids other than salicylic acid, such as sulfonic acid and/or phenol.
  • Detergent compositions comprising, preferably consisting essentially of, at least one calcium phenate-based detergent, preferably at least one overbased calcium phenate-based detergent, have been found to particularly effective in providing oxidation resistance, provided the proportion of the metal salt of a phenol is satisfied. Therefore, detergent compositions comprising only calcium phenate-based detergents, whether neutral or overbased, would be advantageous.
  • the calcium phenate-based detergent may contain one or more metal, preferably calcium, salts of organic acids other than phenol, such as salicylic acid and/or sulfonic acid.
  • the detergent composition in respect of each aspect, is present in the oil composition in an amount, based on surfactant content, of at least 5, preferably at least 10, such as at least 20 or at least 30, more preferably at least 50, most especially at most 75, millimoles of surfactant per kilogram of the oil composition (mmol/kg).
  • the amount of detergent composition, based on surfactant content, in the oil composition is 10 to 15 mmol/kg.
  • Suitable methods for measuring the total metal content include X-ray fluorescence and atomic absorption spectrometry.
  • Suitable methods for determining the amount of metal associated with the organic acids include potentiometric acid titration of the metal salt to determine the relative proportions of the different basic constituents (for example, metal carbonate and metal organic acid salts); hydrolysis of a known amount of metal salt and then the potentiometric base titration of the organic acids to determine the equivalent moles of organic acids; and determination of the non-organic acid anions, such as carbonate, by measuring the CO 2 content.
  • ASTM D3712 may be used to determine the metal associated with the sulfonate.
  • a composition comprises a detergent and one or more co-additives
  • the detergent may be separated from the co-additives, for example, by using dialysis techniques and then the detergent may be analysed as described above to determine the metal ratio.
  • suitable dialysis techniques is given by Amos, R. and Albaugh, E. W. in "Chromatography in Petroleum Analysis” Altgelt, K. H. and Gouw, T. H., Eds., pages 417 to 421, Marcel Dekker Inc., New York and Basel, 1979.
  • EP-A-0 876 449 describes methods for determining the number of moles of a calcium salt of an organic acid, which disclosure is incorporated herein.
  • a skilled person can also calculate the amounts in the final lubricating oil composition from information concerning the amount of raw materials (e.g., organic acids) used to make the detergent(s) and from information concerning the amount of detergent(s) used in the final oil composition.
  • Analytical methods e.g., potentiometric titration and chromatography
  • a dispersant additive (C1) maintains oil-insoluble substances, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge flocculation and precipitation or deposition on metal parts.
  • So-called ashless dispersants are organic materials which form substantially no ash on combustion, in contrast to metal-containing (and thus ash-forming) detergents. Borated metal-free dispersants are also regarded herein as ashless dispersants.
  • Suitable dispersants include, for example, derivatives of long chain hydrocarbyl-substituted carboxylic acids, in which the hydrocarbyl group has a number average molecular weight tends of less than 15,000, such as less than 5000; examples of such derivatives being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • Such hydrocarbyl-substituted carboxylic acids may be reacted with, for example, a nitrogen-containing compound, advantageously a polyalkylene polyamine, or with an ester.
  • Particularly preferred dispersants are the reaction products of polyalkylene amines with alkenyl succinic anhydrides.
  • An ashless succinimide or a derivative thereof obtainable from a polyisobutenylsuccinic anhydride produced from polybutene and maleic anhydride by a thermal reaction method using neither chlorine nor a chlorine atomcontaining compound, is a preferred dispersant.
  • the lubricating oil composition comprises a dispersant additive.
  • dispersancy may be provided by polymeric compounds capable of providing viscosity index improving properties and dispersancy, such compounds are known as a dispersant viscosity index improver additive or a multifunctional viscosity index improver (C1).
  • a dispersant viscosity index improver additive or a multifunctional viscosity index improver (C1).
  • C1 multifunctional viscosity index improver
  • Such polymers differ from conventional viscosity index improvers in that they provide performance properties, such as dispersancy and/or antioxidancy, in addition to viscosity index improvement.
  • Dispersant olefin copolymers and dispersant polymethacrylates are examples of dispersant viscosity index improver additives.
  • Dispersant viscosity index improver additives are prepared by chemically attaching various functional moieties, for example amines, alcohols and amides, onto polymers, which polymers preferably tend to have a number average molecular weight of at least 15,000, such in the range from 20,000 to 600,000, as determined by gel permeation chromatography or light scattering methods.
  • the polymers used may be those described below with respect to viscosity modifiers. Therefore, amine molecules may be incorporated to impart dispersancy and/or antioxidancy characteristics, whereas phenolic molecules may be incorporated to improve antioxidant properties.
  • a specific example therefore, is an inter-polymer of ethylene-propylene post grafted with an active monomer such as maleic anhydride and then derivatized with, for example, an alcohol or amine.
  • EP-A-24146 and EP-A-0 854 904 describe examples of dispersants and dispersant viscosity index improvers, which are accordingly incorporated herein.
  • the lubricating oil composition comprises a dispersant viscosity index improver additive instead of or in addition to a dispersant additive.
  • An antioxidant additive (C2) reduces the tendency of mineral oils to deteriorate in service, evidence of such deterioration being, for example, the production of varnish-like deposits on metal surfaces and of sludge, and viscosity increase.
  • Suitable antioxidant additives include sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof; hindered phenols including alkylene bridged phenols; diphenylamines; phenyl-naphthylamines; and phosphosulfurized or sulfurized hydrocarbons.
  • a preferred antioxidant is an alkylene bridged phenol,
  • antioxidants which may be used in lubricating oil compositions include oil-soluble copper compounds.
  • the copper may be blended into the oil as any suitable oil-soluble copper compound.
  • oil-soluble it is meant that the compound is oil-soluble under normal blending conditions in the oil or additive package.
  • the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid, for example, a C 8 to C 18 fatty acid, an unsaturated acid, or a branched carboxylic acid.
  • oil-soluble copper dithiocarbamates, sulfonates, phenates, and acetylacetonates are basic, neutral or acidic copper Cu I and/or Cu II salts derived from alkenyl succinic acids or anhydrides.
  • Copper antioxidants will generally be employed in an amount of from about 5 to 500 ppm by weight of the copper, in the final lubricating composition.
  • ZDDPs Zinc dihydrocarbyl dithiophosphates
  • Examples of ZDDPs for use in oil-based compositions are those of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 wherein R 1 and R 2 contain from 1 to 18, and preferably 2 to 12, carbon atoms.
  • a ZDDP which has more secondary alkyl groups than primary alkyl groups
  • a ZDDP which has at least 50, preferably at least 75, advantageously 85-100, such as 100, mass % of secondary alkyl groups, based on the mass of the total alkyl groups.
  • Sulfur-containing and molybdenum-containing compounds are also examples of anti-wear additives. Also suitable are ashless phosphorus-containing and sulfur-containing compounds.
  • a preferred type of molybdenum compound is a trinuclear molybdenum compound, which advantageously has a sulfur-containing core.
  • the compound may provide at least 1, for example 1 to 2000, such as 5 to 1000, preferably 20 to 1000, such as 30 to 500, especially 75 to 200, advantagesously 50 to 150, ppm by mass of the Mo, expressed as Mo atoms, based on the mass of the composition.
  • the trinuclear molybdenum compound has a core, preferably a sulfur-containing core, and bonded thereto one or more monoanionic ligands capable of rendering the compound oil-soluble or oil-dispersible, wherein the ratio of the number of molybdenum atoms in the core to the number of said ligands is greater than 1:1, such as 3:2 or greater.
  • the trinuclear molybdenum compound is represented by the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
  • the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble in the oil.
  • the number of carbon atoms in each group will generally range between 1 to 100, preferably from 1 to 30, and more preferably between 4 to 20.
  • Preferred ligands include dialkyldithiophosphate, alkylxanthate, carboxylates, dialkyldithiocarbamate ("dtc"), and mixtures thereof. Most preferred are the dialkyldithiocarbamates.
  • a lubricating oil composition according to the fourth aspect further comprises (C4) a trinuclear molybdenum compound, in a minor amount, but wherein (C1) is a dispersant additive and/or a dispersant viscosity index improver additive.
  • the lubricating oil composition further comprises (C4) a trinuclear molybdenum compound, in a minor amount.
  • WO 98/26030 and US-A-6,232,276 describe trinuclear molybdenum compounds and are, therefore, incorporated herein with respect to their disclosure relating to structures and compositions of trinuclear molybdenum compounds.
  • Viscosity index improvers impart high and low temperature operability to a lubricating oil and permit it to remain shear stable at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures. Therefore, viscosity index improvers are useful in multigrade lubricant oil compositions.
  • Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters, such as polymethacrylates; poly(ethylene-co-propylene) polymers and closely related modifications (so called olefin copolymers); hydrogenated poly(styrene-co-butadiene or -isoprene) polymers and modifications; and esterified poly(styrene-co-maleic anhydride) polymers.
  • Oil-soluble viscosity modifying polymers generally have number average molecular weights of at least 15,000 to 1,000,000, preferably 20,000 to 600,000, as determined by gel permeation chromatography or light scattering methods. The disclosure in Chapter 5 of "Chemistry & Technology of Lubricants", edited by R.M. Mortier and S.T. Orzulik, First edition, 1992, Blackie Academic & Professional, is incorporated herein.
  • co-additives suitable in the present invention include corrosion inhibitors, friction modifiers, rust inhibitors or rust prevention agents, pour point depressants, demulsifiers, and anti-foaming agents.
  • additives may provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
  • each additive is typically blended into the base oil in an amount which enables the additive to provide its desired function.
  • Representative effective amounts of such additives, when used in lubricants, are as follows: Additive Mass % a.i. (Broad) Mass % a.i.
  • Viscosity Index Improver 0.01-6 0.01-4 Corrosion Inhibitor 0.01-5 0.01-1.5 Antioxidant additive 0.01-5 0.01-3 Friction Modifier 0.01-5 0.01-1.5 Dispersant additive 0.1-20 0.1-8 Dispersant Viscosity Index Improver additive 0.01 -5 0.05-5 Detergent composition 0.01-10 0.01-6 Antiwear additive 0.01-6 0.01-4 Pour Point Depressant 0.01-5 0.01-1.5 Rust Inhibitor 0.001-0.5 0.01-0.2 Anti-Foaming Agent 0.001-0.3 0.001-0.15 Demulsifier 0.001-0.5 0.01-0.2
  • the additives may be incorporated into a base oil in any convenient way.
  • each of the additive can be added directly to the oil by dispersing or dissolving it in the oil at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • additive packages also known as additive compositions or concentrates
  • additives comprising the additives
  • several additives with the exception of viscosity modifiers, multifuntional viscosity modifiers and pour point depressants, can be added simultaneously to the base oil to form the lubricating oil composition.
  • Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
  • one or more detergents may be added to small amounts of a carrier fluid or diluent, such as a base oil or another compatible solvent together with other desirable additives to form additive packages containing active ingredients in an amount, based on the mass of the additive package, of, for example, from about 2.5 to about 90, preferably from about 5 to about 75, most preferably from about 8 to about 60, mass %, of additives in the appropriate proportions with the remainder being carrier fluid or diluent.
  • the amount of phosphorus is less than 0.5, more preferably less than 0.3, mass %, of phosphorus, based on the mass of the additive composition. In a preferred embodiment, the amount of phosphorus is at least 0.01 mass %, based on the mass of the additive composition.
  • the additive composition of the seventh aspect has an amount of sulfur, independently of the amount of phosphorus, of less than 2.0, more preferably less than 2.00 or less than 1.75, mass %, based on the mass of the additive composition.
  • the amount of sulfur is at least 0.01 mass %, based on the mass of the additive composition.
  • the amount of additives in the final lubricating oil composition is generally dependent on the type of the oil composition, for example, a heavy duty diesel engine lubricating oil composition has 2 to 20, preferably 7 to 18, more preferably 8 to 16, such as 8 to 14, mass % of additives based on the mass of the oil composition.
  • a passenger car engine lubricating oil composition for example, a gasoline or a diesel engine oil composition, may have a lower amount of additives, for example 3 to 10, preferably 4 to 9, especially 6 to 8, mass % of additives based on the mass of the oil composition.
  • the proportions of the (a) to (e) in an additive composition of the seventh aspect are such so to provide a lubricating oil composition, as defined in any one of the third to sixth aspect, when the oil composition contains 2 to 20 mass % of all of (a) to (e).
  • the method of preparing the oil composition according to the ninth aspect can involve admixing component (A) and an additive package that comprises components (B) and (C).
  • the proportions of the (a) to (e) in an additive composition of the seventh aspect are such so to provide a composition having less than 0.09 mass % of phosphorus and at most 0.5 mass % of sulfur, when the additive composition is diluted in a way that the diluted additive composition contains 3.75 mass % of components (b) to (d), based on the mass of the diluted composition.
  • the proportions of (a) to (e) are such as to also provide a composition having less than 2 mass % of sulfated ash.
  • the additive compositions of the present invention give a sulfated ash level of at most 10, more preferably at most 8, advantageously at most 7, mass %.
  • the amount of anti-oxidant additives in the additive composition is in the range of from 1 to 20 parts, the amount of phosphorus-containing and/or sulfur-containing additives in the additive composition is in the range of from 1 to 9 parts.
  • interaction may take place between any two or more of the additives, including any two or more detergents, after they have been incorporated into the oil composition.
  • the interaction may take place in either the process of mixing or any subsequent condition to which the composition is exposed, including the use of the composition in its working environment.
  • Interactions may also take place when further auxiliary additives are added to the compositions of the invention or with components of oil.
  • Such interaction may include interaction which alters the chemical constitution of the additives.
  • the compositions of the invention include compositions in which interaction, for example, between any of the additives, has occurred, as well as compositions in which no interaction has occurred, for example, between the components mixed in the oil.
  • hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • oil-soluble or “oil-dispersible”, as used herein, does not mean that the additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. They do mean, however, that the additives are, for instance, soluble or stable dispersible in the oil to an extent sufficient to exert their intended effect in the environment in which the oil composition is employed. Moreover, the additional incorporation of other additives such as those described above may affect the solubility or dispersibility of the additives.
  • Major amount means in excess of 50 mass % of the composition.
  • Minor amount means less than 50 mass % of the composition, both in respect of the stated additive and in respect of the total mass % of all of the additives present in the composition, reckoned as active ingredient of the additive or additives.
  • SAE Society of Automotive Engineers, who classify lubricants by viscosity grades.
  • the amount of phosphorus, sulfur and molybdenum in the lubricating oil composition is measured according to ASTM D5185; the amount of nitrogen in the lubricating oil composition is measured according to ASTM D4629; and the amount of chlorine in the lubricating oil composition is measured according to Institute of Petroleum Proposed Method AK/99.
  • Lubricating oil compositions respectively containing 0.07, 0.04 and 0, mass % of phosphorus, were prepared by blending methods known in the art.
  • the oil compositions contained a detergent composition, a dispersant additive, an anti-oxidant additive, and an anti-wear additive (e.g., a zinc dithiophosphate) in varying amounts, including none in one case, to provide the different phosphorus levels.
  • Each oil composition was a SAE 5W30 lubricating oil composition.
  • Comparative Examples 1 to 3 contained, as detergents, a phenate detergent and a sulfonate detergent only (in a surfactant ratio of about 73:27), and, as antioxidant, a phenolic antioxidant only.
  • Examples 1 to 3 of the invention contained, as detergents, a salicylate detergent only and, as antioxidant, an aminic antioxidant only. Table 1 shows the properties of the compositions.
  • the film thickness and wear performance of the compositions were measured on an elastohydrodynamic film thickness rig, a traction rig adapted to the pin on disc option, and in a four ball extreme pressure test.
  • the elastohydrodynamic rig measures film thickness between a steel ball and a coated glass disc that are in rolling contact.
  • the test conditions are a varying rolling speed; a temperature of 100 °C; 100 % rolling contact (0 % slide/roll ratio) and a load of 20 N.
  • Full details of the apparatus and test procedure are described in Tribology International, 33 (2000), 241-247; SAE 962037; SAE 961142; and SAE 962640.
  • Oil compositions that exhibit larger film thickness are more likely to provide better wear performance; this is because thicker films are more likely to a) separate contacting surfaces and b) shear at lower stress than the underlying metal, thereby mitigating adhesive wear.
  • the traction rig is as described in SAE 962037, SAE 961142, and SAE 962640, but where the steel ball is replaced by a steel pin of 0.5 mm diameter which contacts the steel disc at a constant load and temperature as described in SAE 981406.
  • the disc is driven at a constant speed and the wear is measured by a linear voltage displacement transducer.
  • the test conditions are: a time of 1 hour; a temperature of 100 °C, a load of 30 N; and a sliding speed of 1 m/s.
  • the apparatus used in the four ball extreme pressure test is that used in the industry test IP239.
  • the conditions are specified in the Peugeot D55-1136 method, and briefly these are: a rotating speed of 1500 rpm; a time of 60 seconds; and a load of either 100kg or 85 kg.
  • Table 2 shows that the films formed in the test on Examples 1 to 3 (salicylate-containing oil compositions) are thicker than those formed in the corresponding Comparative Examples 1 to 3.
  • the salicylate-containing oil compositions show a surprising and significant advantage at lower phosphorus levels.
  • the salicylate-containing oil compositions substantially maintain the film thickness as the phosphorus level is reduced. This effect is demonstrated in the elastohydrodynamic rig at three different rolling speeds at least.
  • the data from the traction rig adapted to the pin on disc option in Table 3 support the superior and unexpected performance of salicylate-containing oil compositions at low phosphorus levels: the salicylate-containing oil compositions exhibit less wear in compositions containing 0.04 mass % or less of phosphorus.
EP02076732.3A 2001-05-11 2002-05-02 Additifs anti-usures et antioxydants pour compositions d'huiles lubrifiantes Expired - Lifetime EP1262538B1 (fr)

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EP01201752A EP1256619A1 (fr) 2001-05-11 2001-05-11 Composition d'huile lubrifiante
GB0128734 2001-11-30
GB0128734A GB0128734D0 (en) 2001-11-30 2001-11-30 Lubricating oil composition
EP02076732.3A EP1262538B1 (fr) 2001-05-11 2002-05-02 Additifs anti-usures et antioxydants pour compositions d'huiles lubrifiantes

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EP1323816A1 (fr) * 2001-12-21 2003-07-02 Infineum International Limited Compositions d'huiles lubrifiantes pour moteur diesel de grande puissance
WO2005068590A1 (fr) 2004-01-05 2005-07-28 The Lubrizol Corporation Composition lubrifiante pratiquement exempte de zddp
SG137683A1 (en) * 2003-05-22 2007-12-28 Chevron Oronite Co Unsulfurized, carboxylate-containing additive for lubricating oils
RU2456335C1 (ru) * 2011-06-09 2012-07-20 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (ОАО "ВНИИ НП") Моторное масло
US9469825B2 (en) 2015-03-12 2016-10-18 Afton Chemical Corporation Lubricant composition for automatic transmissions
US11578287B1 (en) 2021-12-21 2023-02-14 Afton Chemical Corporation Mixed fleet capable lubricating compositions
US11807827B2 (en) 2022-01-18 2023-11-07 Afton Chemical Corporation Lubricating compositions for reduced high temperature deposits
US11912955B1 (en) 2022-10-28 2024-02-27 Afton Chemical Corporation Lubricating compositions for reduced low temperature valve train wear
US11926804B1 (en) 2023-01-31 2024-03-12 Afton Chemical Corporation Dispersant and detergent systems for improved motor oil performance
US11970671B2 (en) 2022-07-15 2024-04-30 Afton Chemical Corporation Detergent systems for oxidation resistance in lubricants

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EP3562921B1 (fr) * 2016-12-27 2022-04-27 The Lubrizol Corporation Composition lubrifiante comportant de la dianiline n-alkylée

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1323816A1 (fr) * 2001-12-21 2003-07-02 Infineum International Limited Compositions d'huiles lubrifiantes pour moteur diesel de grande puissance
SG137683A1 (en) * 2003-05-22 2007-12-28 Chevron Oronite Co Unsulfurized, carboxylate-containing additive for lubricating oils
WO2005068590A1 (fr) 2004-01-05 2005-07-28 The Lubrizol Corporation Composition lubrifiante pratiquement exempte de zddp
RU2456335C1 (ru) * 2011-06-09 2012-07-20 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (ОАО "ВНИИ НП") Моторное масло
US9469825B2 (en) 2015-03-12 2016-10-18 Afton Chemical Corporation Lubricant composition for automatic transmissions
US11578287B1 (en) 2021-12-21 2023-02-14 Afton Chemical Corporation Mixed fleet capable lubricating compositions
US11807827B2 (en) 2022-01-18 2023-11-07 Afton Chemical Corporation Lubricating compositions for reduced high temperature deposits
US11970671B2 (en) 2022-07-15 2024-04-30 Afton Chemical Corporation Detergent systems for oxidation resistance in lubricants
US11912955B1 (en) 2022-10-28 2024-02-27 Afton Chemical Corporation Lubricating compositions for reduced low temperature valve train wear
US11926804B1 (en) 2023-01-31 2024-03-12 Afton Chemical Corporation Dispersant and detergent systems for improved motor oil performance

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