EP1310549B1 - Borenthaltende Schmierölzusammensetzung mit niedrigem Schwefel- und Phosphor-Gehalt - Google Patents

Borenthaltende Schmierölzusammensetzung mit niedrigem Schwefel- und Phosphor-Gehalt Download PDF

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Publication number
EP1310549B1
EP1310549B1 EP02257525A EP02257525A EP1310549B1 EP 1310549 B1 EP1310549 B1 EP 1310549B1 EP 02257525 A EP02257525 A EP 02257525A EP 02257525 A EP02257525 A EP 02257525A EP 1310549 B1 EP1310549 B1 EP 1310549B1
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EP
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Prior art keywords
mass
composition
ppm
boron
oil composition
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EP02257525A
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English (en)
French (fr)
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EP1310549A1 (de
Inventor
Robert Robson
Roger Woodgate Glyde
Alisdair James Brown
Simon Siu Ming Chung
Stephen Arrowsmith
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Infineum International Ltd
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Infineum International Ltd
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Priority claimed from EP01309510A external-priority patent/EP1310548A1/de
Priority claimed from EP02250224A external-priority patent/EP1329496A1/de
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Priority to EP02257525A priority Critical patent/EP1310549B1/de
Publication of EP1310549A1 publication Critical patent/EP1310549A1/de
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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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2030/10—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
    • C10N2030/40—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
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This invention relates to lubricating oil compositions, more especially to compositions suitable for use in piston engine, especially gasoline (spark-ignited) and diesel (compression-ignited), crankcase lubrication.
  • Such compositions may be referred to as crankcase lubricants.
  • ZDDPs zinc dialkyldithiophosphates
  • a problem arising from the use of ZDDPs is their phosphorus content: phosphorus derivatives deriving from the ZDDPs can poison the components of exhaust gas catalytic converters.
  • Catalytic converters are used to reduce pollution and to meet governmental regulations requiring reduction in the levels of undesirable gases, such as hydrocarbons, carbon monoxide, and oxides of nitrogen, from internal engine combustion exhaust emissions.
  • Such converters use catalysts which are installed in the exhaust streams, e.g. the exhausts of automobiles, to treat the undesirable gases.
  • Phosphorus derivatives, such as decomposition products of ZDDPs can be carried into the exhaust, where they are believed to poison the catalyst. Accordingly, the use of engine oils containing phosphorus additives may substantially reduce the life and effectiveness of catalytic converters.
  • EP1167497 discloses a lubricating oil composition having (weight %) sulfur (0.01-0.3), phosphorus (0.01-0.1), and giving sulfated ash (0.1-1), and comprising (weight %): (a) major amount of mineral base oil; (b) ashless alkenyl- or alkyl-succinimide dispersant (0.01-0.3);(c) detergent containing non-sulfurized alkali metal or alkaline earth metal salt of alkyl salicylic acid and/or alkyl phenol derivative (0.1-1);(d) zinc dialkyldithiophosphate (0.01-0.1); and (e) oxidation inhibitor such as phenol or amine compounds (0.01-5).
  • the invention provides a crankcase lubricating oil composition
  • a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 600 ppm by mass of boron, less than 200 ppm by mass of phosphorus and less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, and wherein the lubricating oil composition does not contain a borate ester additive.
  • the invention provides a crankcase lubricating oil composition
  • a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive, a detergent additive composition and one or more co-additives, wherein the lubricating oil composition has greater than 600 ppm by mass of boron, less than 200 ppm by mass of phosphorus and less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, wherein the lubricating oil composition does not contain a borate ester additive, and provided that the detergent additive composition comprises at least two detergents, which detergents may comprise the same metal or two different metals.
  • the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 600 ppm or boron, less than 200 ppm by mass of phosphorus and less than 4000, by mass ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 2 to 20 mass % of the additives, and wherein the additive composition does not comprise a borate ester additive.
  • the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive, a detergent additive composition comprising at least two detergents of at least two metals and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 600 ppm by mass of boron, less than 200 ppm by mass of phosphorus and less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 2 to 20 mass % of the additives, wherein the composition does not contain a borate ester additive.
  • the invention provides a method for conferring wear resistance (anti-wear properties) to a crankcase lubricating oil composition that contains less than 200 ppm by mass of phosphorus and less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, by provision in the oil composition of a boron-containing additive to provide greater than 600 ppm by mass of boron based on the mass of the oil composition, wherein the composition does not contain a borate ester additive.
  • the invention provides a method of lubricating the crankcase of a spark-ignited or a compression-ignited internal combustion engine which comprises supplying to the engine a lubricating oil composition according to the first or second aspect of the invention.
  • the invention provides the use of an effective amount of a boron-containing additive in a crankcase lubricating oil composition that contains less than 200 ppm by mass of phosphorus and less than 4000 ppm by mass of sulfur, based on the mass of the oil composition, to provide wear resistance, in particular in the Peugeot TU3M Scuffing Test and/or Sequence IVA Test.
  • An effective amount is preferably an amount sufficient to provide at least 600 ppm by mass of boron based on mass of the oil composition.
  • the invention provides the use of 600 ppm by mass of boron of a boron-containing additive and at most 400 ppm by mass of molybdenum of a molybdenum-containing additive in a lubricating oil composition that contains less than 200 ppm by mass of phosphorus and less than 4000 ppm by mass of sulfur, based on the mass of the oil composition, to provide friction-reducing performance and/or anti-oxidancy performance to the oil composition.
  • the lubricating oil compositions of this invention comprise defined individual, i.e., separate, components that may or may not remain the same chemically before and after mixing.
  • various components of the composition essential as well as optional and customary, may react under the conditions of formulation, storage or use, and that the invention also provides the product obtainable or obtained as a result of any such reaction.
  • the amount of phosphorus, sulfur, boron or molybdenum in the lubricating oil composition is measured according to ASTM D5185.
  • the amount of phosphorus in the lubricating oil composition may be less than 100, ppm, based on the mass of the oil composition. More preferably, it is zero.
  • the amount of phosphorus in the lubricating oil composition is preferably less than 200, advantageously less than 100, ppm, based on the mass of the oil composition. More preferably, it is zero.
  • the amount of phosphorus in the lubricating oil composition is preferably less than 200, advantageously less than 100, ppm, based on the mass of the oil composition. More preferably, it is zero.
  • the amount of sulfur in the lubricating oil composition is preferably at most 3000, more preferably at most 2500, ppm by mass, based on the mass of the oil composition; especially the amount of sulfur is at most 2000, or at most 1500, ppm by mass; advantageously the amount of sulfur is less than 1000, or less than 700, ppm. In an embodiment, the amount of sulfur is less than 500 ppm, preferably the amount of sulfur is zero.
  • the phosphorus in the oil composition is derived from a phosphorus-containing additive, such as a ZDDP that may be present.
  • the sulfur can be derived from the oil of lubricating viscosity, such as Group I, II or III basestock; the diluent oil or carrier oil, which is used as a carrier fluid for the additive components and additive compositions; and any sulfur-containing additives, for example, ZDDPs and sulfonate detergents.
  • the defined amount of phosphorus is in respect of the amount of phosphorus derived from ZDDP that is present.
  • the amount of boron independently of the amount of sulfur or phosphorus, with respect to the first or third aspect is preferably greater than 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200, 1500 or 2000, ppm.
  • the amount of boron does not exceed 10,000, preferably not greater than 7500, more preferably not greater than 5000, such as not greater than 3000, ppm, based on the mass of the oil composition.
  • the amount of boron independently of the amount of sulfur or phosphorus, with respect to the second, fourth, fifth, seventh or eigth aspect is preferably greater than 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200, 1500 or 2000, ppm.
  • the amount of boron does not exceed 10,000, preferably not greater than 7500, more preferably not greater than 5000, such as not greater than 3000, ppm, based on the mass of the oil composition.
  • the boron in the oil composition is derived from a boron-containing additive.
  • a copper-containing compound such as a copper carboxylate, is substantially absent or a zinc dithiocarbamate is substantially absent.
  • a molybdenum-containing additive for example a molybdenum dithiocarbamate is present in the oil composition, then the amount of molybdenum in the oil composition is, independently of the amount of boron, phosphorus and sulfur, at most 1000, preferably at most 750, more preferably at most 500, such as at most 400, especially in the range 300 to 50, advantageously in the range 75 to 275, more advantageously in the range 100 to 250, ppm by mass, based on the mass of the oil composition.
  • the lubricating oil composition has less than 1.5, especially less than 1.3, advantageously in the range of 0.01 to 1.0, such as in the range from 0.5 to 0.8, mass % of sulfated ash, according to the method ASTM D874.
  • the lubricating oil composition is a multigrade identified by the viscometric descriptor SAE 15WX, SAE 10WX, SAE 5WX or SAE 0WX, where X represents any one of 20, 30, 40 and 50; the characteristics of the different viscometric grades can be found in the SAE J300 classification.
  • the lubricating oil composition is in the form of an SAE 10WX, SAE 5WX or SAE 0WX, preferably in the form of an SAE 5WX or SAE 0WX, wherein X represents any one of 20, 30, 40 and 50.
  • X is 20 or 30.
  • the lubricating oil compositions of each aspect of the invention are suitable for lubricating an internal combustion engine, such as a passenger car engine or a heavy duty diesel engine.
  • passenger car engines are light duty diesel engines and gasoline engines.
  • the heavy duty diesel engines are used in land-based vehicles, 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 vehichs.
  • 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 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 first, second or third aspect.
  • API American Petroleum Institute
  • API Association des Constructeur Europeén d'Autombile
  • JASO Japanese Standards Organisation
  • Global which contains tests and performance levels from ACEA, API and JASO specifications.
  • 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 oil of lubricating viscosity or lubricating oil can be a synthetic or mineral oil of lubricating viscosity selected from the group consisting of Group I, II, III, IV and V basestocks, and a mixture containing any two or more thereof.
  • Basestocks may be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
  • API 1509 "Engine Oil Licensing and Certification System” Fourteenth Edition, December 1996 states that all basestocks are divided into five general categories:
  • the lubricating oil is selected from any one of Group I to V basestocks and mixtures thereof.
  • test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.
  • Boron-containing additives may be prepared by reacting a boron compound with an oil-soluble or oil-dispersible additive or compound.
  • Boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acid such as boronic acid, boric acid, tetraboric acid and metaboric acid, boron hydrides and boron.
  • boron-containing additives include a borated dispersant; a borated dispersant VI improver; an alkali metal or a mixed alkali metal or an alkaline earth metal borate; a borated overbased metal detergent; a borated epoxide; and a borate amide.
  • Borated dispersants may be prepared by boration of succinimide, succinic ester, benzylamine and their derivatives, each of which has an alkyl or alkenyl group of molecular weight of 700 to 3000. Processes for manufacture of these additives are known to those skilled in the art. A preferred amount of boron contained in these dispersants is 0.1 to 5 mass % (especially 0.2 to 2 mass %). A particularly preferable borated dispersant is a succinimide derivative of boron, for example borated polyisobutenyl succinimide.
  • Alkali metal and alkaline earth metal borates are generally hydrated particulate metal borates, which are known in the art.
  • Alkali metal borates include mixed alkali and alkaline earth metal borates. These metal borates are available commercially.
  • Representative patents describing suitable alkali metal and alkaline earth metal borates and their methods of manufacture include U.S. 3,997,454; 3,819,521; 3,853.772; 3,907,601; 3,997,454; and 4,089,790.
  • Boron-containing additives include borated fatty amines.
  • the borated amines may be prepared by reacting one or more of the above boron compounds with one or more of fatty amines, e.g., an amine having from four to eighteen carbon atoms. They may be prepared by reacting the amine with the boron compound at a temperature in the range of from 50 to 300, preferably from 100 to 250, °C, and at a ratio from 3:1 to 1:3 equivalents of amine to equivalents of boron compound.
  • Borated fatty epoxides are generally the reaction product of one or more of the above boron compounds with at least one epoxide.
  • the epoxide is generally an aliphatic epoxide having from 8 to 30, preferably from 10 to 24, more preferably from 12 to 20, carbon atoms.
  • Examples of useful aliphatic epoxides include heptyl epoxide and octyl epoxide. Mixtures of epoxides may also be used, for instance commercial mixtures of epoxides having from 14 to 16 carbon atoms and from 14 to 18 carbon atoms.
  • the borated fatty epoxides are generally known and are described in U.S. Patent 4,584,115.
  • Borated overbased metal detergents are known in the art where the borate substitutes the carbonate in the core either in part or in full.
  • a preferred boron-containing additive is a borated dispersant, for example, a borated polyisobutenyl succinimide wherein the average number molecular weight (M ⁇ n) of the polybutenyl backbone is in the range from 700 to 1250.
  • a detergent additive composition which comprises one or more detergents, may be provided in the lubricating oil composition.
  • 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 usually based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
  • Organic acids useful in present invention typically have one or more functional groups, such as OH or COOH or SO 3 H, and a hydrocarbyl substituent. Examples of organic acids include sulfonic acids, phenols and sulfurised derivatives thereof, and carboxylic acids.
  • the metal detergent may be neutral or overbased, which terms are known in the art.
  • the detergent additive composition may comprise one or more neutral detergents or one or more overbased detergents or a mixture thereof.
  • the metals are preferably selected from Group 1 and Group 2 metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
  • the detergent additive composition in respect of each aspect of the invention, comprises a metal salt of an aromatic carboxylic acid, for example a salicylate-based detergent, such as calcium salicylate.
  • the detergent additive 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. More preferably the proportion of the metal salt of an aromatic carboxylic acid is at least 60 or at least 70 mole %; more preferably at least 80 or at least 90 mole %, based on the moles of the metal salts of organic acids in the detergent additive composition.
  • the detergent additive 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 additive composition comprises only aromatic carboxylic acids as the organic acids.
  • aromatic carboxylic acids are salicylic acids and sulphurised derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof. Especially preferred are salicylic acids.
  • the detergent additive composition comprises one or more detergents of the same metal, for example calcium or magnesium, preferably calcium; more preferably the detergents are of different surfactant types, such as calcium salicylate and calcium sulfonate.
  • the detergent additive composition comprises at least two detergents of at least different two metals, for example a neutral or overbased magnesium detergent and at least one other metal detergent, e.g., a neutral or overbased calcium detergent and/or neutral or overbased sodium detergent.
  • Preferred detergent additive compositions in respect of each aspect of the invention comprise a mixture of calcium and magnesium detergents.
  • Detergent additive compositions comprising only salicylate detergents, whether neutral or overbased, are particularly advantageous.
  • Surfactants that may also be used include aliphatic carboxylates; sulfonates; phenates, non-sulfurised or sulfurised; thiophosphonates; and naphthenates.
  • a detergent in the form of a hybrid complex detergent wherein the basic material is stabilised by more than one type of surfactant.
  • a single type of organic acid may contain a mixture of organic acids of the same type.
  • a sulphonic acid may contain a mixture of sulphonic acids of varying molecular weights.
  • Such an organic acid composition is considered as one type.
  • complex detergents are distinguished from mixtures of two or more separate overbased detergents, an example of such a mixture being one of an overbased calcium salicylate detergent with an overbased calcium phenate 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"
  • the proportion of one surfactant to another in a complex detergent is not critical.
  • Preferred complex detergents are salicylate-based detergents, for example, "phenalates” and salicylate-based detergents disclosed in any one of International Patent Application Publication Nos. 9746643/4/5/6 and 7.
  • 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 Total Base Number
  • the detergent additive composition consists of metal salicylate detergents
  • the salicylate is either calcium salicylate or a mixture of calcium and magnesium salicylates. More preferably, at least one or each metal salicylate detergent is overbased.
  • both calcium and magnesium salicylates are present, more calcium salicylate than magnesium salicylate is preferably be present, based on the mass of the respective metals.
  • the detergent additive composition comprises two or more metal detergents of different surfactant types, it is preferred that the detergents have the same metal, for example, calcium.
  • the total amount of metal derived from the metal detergents in the lubricating oil composition is at most 2700 ppm, based on the mass of the oil composition.
  • Suitable methods for measuring the total metal content are well known in the art and include X-ray fluorescence and atomic absorption spectrometry.
  • Means for determining the amount of metal salt of an organic acid are known to those skilled in the art.
  • a skilled person can 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
  • can also be used to determine the amounts of metal salts of organic acid e.g., in the case of a metal sulphonate, ASTM D3712 may be used to determine the metal associated with the sulphonate).
  • the oil-soluble or oil-dispersible molybdenum molubdenum-containing additive comprises one or more oil-soluble or oil-dispersible molybdenum compounds.
  • the molybdenum compound is a molybdenum-sulfur compound.
  • the molybdenum-sulfur compounds useful in the present invention may be mononuclear or polynuclear.
  • the compound in the event that the compound is polynuclear, the compound contains a molybdenum core consisting of non-metallic atoms, such as sulfur, oxygen and selenium, preferably consisting essentially of sulfur.
  • one or more ligands are bonded to a molybdenum atom in the compound.
  • the bonding of the ligands includes bonding by electrostatic interaction as in the case of a counter-ion and forms of bonding intermediate between covalent and electrostatic bonding.
  • Ligands within the same compound may be differently bonded. For example, a ligand may be covalently bonded and another ligand may be electrostatically bonded.
  • the or each ligand is monoanionic and examples of such ligands are dithiophosphates, dithiocarbamates, xanthates, carboxylates, thioxanthates, phosphates and hydrocarbyl, preferably alkyl, derivatives thereof.
  • the ratio of the number of molybdenum atoms, for example, in the core in the event that the molybdenum-sulfur compound is a polynuclear compound, to the number of monoanionic ligands, which are capable of rendering the compound oil-soluble or oil-dispersible is greater than 1 to 1, such as at least 3 to 2.
  • the molybdenum-sulfur compound's oil-solubility or oil-dispersibility may be influenced by the total number of carbon atoms present among all of the compound's ligands.
  • the total number of carbon atoms present among all of the hydrocarbyl groups of the compound's ligands typically will be at least 21, e.g. 21 to 800, such as at least 25, at least 30 or at least 35.
  • the number of carbon atoms in each alkyl group will generally range between 1 to 100, preferably 1 to 40, and more preferably between 3 and 20.
  • molybdenum-sulfur compounds include dinuclear molybdenum-sulfur compounds and trinuclear molybdenum-sulfur compounds.
  • R 1 to R 4 independently denote a straight chain, branched chain or aromatic hydrocarbyl group having 1 to 24 carbon atoms; and X 1 to X 4 independently denote an oxygen atom or a sulfur atom.
  • the four hydrocarbyl groups, R 1 to R 4 may be identical or different from one another.
  • the molybdenum-sulfur compound is an oil-soluble or oil-dispersible trinuclear molybdenum-sulfur compound.
  • examples of trinuclear molybdenum-sulfur compounds are disclosed in WO98/26030, WO99/31113, WO99/66013, EP-A-1 138 752, EP-A-1 138 686 and European patent application no. 02078011.
  • the molybdenum-sulfur compound has a core of the structures depicted in (I) or (II): or
  • Each core has a net electrical charge of +4.
  • the trinuclear molybdenum-sulfur compounds are represented by the formula Mo 3 S k E x L n A p Q z , wherein:
  • trinuclear molybdenum-sulfur compound will require selection of appropriate ligands (L) and other anions (A), depending on, for example, the number of sulfur and E atoms present in the core, i.e. the total anionic charge contributed by sulfur atom(s), E atom(s), if present, L and A, if present, must be -12.
  • Q examples include water, alcohol, amine, ether and phosphine. It is believed that the electron-donating compound, Q, is merely present to fill any vacant coordination sites on the trinuclear molybdenum-sulfur compound.
  • A can be of any valence, for example, monovalent and divalent and include disulfide, hydroxide, alkoxide, amide and, thiocyanate or derivative thereof; preferably A represents a disulfide ion.
  • L is monoanionic ligand, such as dithiophosphates, dithiocarbamates, xanthates, carboxylates, thioxanthates, phosphates and hydrocarbyl, preferably alkyl, derivatives thereof.
  • n is 2 or more, the ligands can be the same or different.
  • k is 4 or 7
  • n is either 1 or 2
  • L is a monoanionic ligand
  • p is an integer to confer electrical neutrality on the compound based on the anionic charge on A and each of x and z is 0.
  • k is 4 or 7
  • L is a monoanionic ligand
  • n is 4 and each of p, x and z is 0.
  • the molybdenum-containing additive comprises trinuclear molybdenum core and bonded thereto a ligand, preferably a mono-anionic ligand, such as a dithiocarbamate, capable of rendering the core oil-soluble or oil-dispersible.
  • a ligand preferably a mono-anionic ligand, such as a dithiocarbamate, capable of rendering the core oil-soluble or oil-dispersible.
  • the molybdenum-containing additive may also comprise either negatively molybdenum species or positively molybdenum species or both negatively and positively charged molybdenum species.
  • the molybdenum-sulfur cores may be interconnected by means of one or more ligands that are multidentate, i.e. a ligand having more than one functional group capable of binding to a molybdenum atom, to form oligomers.
  • Molybdenum-sulfur additives comprising such oligomers are considered to fall within the scope of this invention.
  • molybdenum compounds include molybdenum carboxylates and molybdenum nitrogen complexes, both of which may be sulfurised.
  • co-additives may be present to meet particular requirements.
  • examples of such include viscosity index improvers, corrosion inhibitors, detergents other than those mentioned, metal rust inhibitors, pour point depressants, anti-foaming agents, dispersants other than those mentioned, anti-wear agents, oxidation inhibitors or anitoxidants, and friction modifiers.
  • the preparation of an additive composition is a convenient method of adding the additives to a lubricating oil in order to yield a lubricating oil 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 preferably has 7 to 20, more preferably 8 to 16, such as 8 to 14, mass % of additives, based on the mass of the oil composition. A 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, tends to have a lower amount of additives, for example 2 to 10, such as 3 or 4 to 10, preferably 3 to 9, especially 6 to 8, mass % of additives, based on the mass of the oil composition.
  • crankcase lubricating oil compositions each satisfying the 5W30 viscosity grade, were prepared by methods known in the art.
  • Two, Examples 1 and 2 are examples of the invention, and two, Examples A and B, are comparative examples.
  • the compositional details of the examples are shown in Table 1.
  • Table 1 Elemental Content (ppm by mass) Ex. A Ex. B Ex. 1 Ex.
  • the sulfated ash content of each composition in Table 1 is on or about 1 mass %. In all other relevant respects, the four compositions are comparable.
  • Table shows that superior wear results are obtained by inclusion of boron at broadly similar sulfur levels and in the absence of phosphorus, i.e., comparing the results for Examples 1 and 2 with those for Example A. They also show that inclusion of boron gives rise to better overall wear results than a boron-free composition containing higher levels of both phosphorus and sulfur, i.e. comparing the results for Examples 1 and 2 with those for Example B.
  • Multigrade crankcase lubricating oil compositions comprising a boron-containing additive and, optionally a molybdenum-containing additive were also prepared by methods known in the art.
  • Examples C to G are comparative examples and Examples 3 to 6 are examples of the invention.
  • the compositional details of the oil compositions are shown in Table 3.
  • Examples C to E each of which contained no molybdenum but an incrementally increasing amount of boron from about 300 to about 900 ppm, did not show any improvement in anti-oxidancy. Similar observations are noted for Examples F, G and Example 3, each of which contained about 100 ppm of molybdenum and an incrementally increasing amount of boron from about 300 to about 900 ppm. In contrast, a surprising improvement in the anti-oxidancy behaviour is observed in Examples 4 to 6, each of which contained a higher comparable amount of molybdenum, when the amount of boron is incrementally increased from about 300 to about 900 ppm.
  • Table 3 also shows the friction-reducing performance of the oil compositions.
  • Examples C to E demonstrated comparable performance although the amount of boron is incrementally increased from about 300 to about 900 ppm. A similar trend is apparent for Examples F and G, but Example 3 containing about 900 ppm of boron and about 100 ppm of molybdenum showed an improvement in friction-reduction.
  • Examples 4 to 6 demonstrated better friction-reducing behaviour as the amount of boron is increased from about 300 to about 900 ppm while the amount of molybdenum is kept constant at a higher comparable amount. In particular, it has been noted, in Examples 4 to 6, that the induction period for the formation of the low co-efficient of friction films is reduced as the amount of boron is increased and thus leading to a better friction performance.
  • the sulfated ash content of each of the oil composition (Ex. C to G and Ex. 3 to 6) is less than 1 %; the sulfur content, derived from the basestock and diluent, of each of the oil compositions is less than 1150 ppm by mass; and in all other relevant respects the oil compositions are comparable.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (13)

  1. Kurbelgehäuseschmierölzusammensetzung, die Öl mit Schmierviskösität in größerer Menge, und, in jeweils geringeren Mengen, borhaltiges Additiv und ein oder mehrere Co-Additive umfasst oder durch Mischen derselben hergestellt ist, wobei die Schmierölzusammensetzung mehr als 600 Massen-ppm Bor, weniger als 200 Massen-ppm Phosphor und weniger als 4000 Massen-ppm Schwefel aufweist, bezogen auf die Masse der Ölzusammensetzung, und wobei die Schmierölzusammensetzung kein Boratester-Additiv umfasst.
  2. Kurbelgehäuseschmierölzusammensetzung nach Anspruch 1, die eine Detergensadditivzusammensetzung umfasst, die mindestens zwei Detergenzien umfasst, wobei die Detergenzien dieselben Metalle oder mindestens zwei verschiedene Metalle umfassen können.
  3. Zusammensetzung nach Anspruch 1 oder 2, die ferner molybdänhaltiges Additiv in einer geringeren Menge, die höchstens 400 Massen-ppm Molybdän bereitstellt, umfasst oder durch Mischen derselben hergestellt ist.
  4. Zusammensetzung nach Anspruch 1, 2 oder 3, wobei das borhaltige Additiv ausgewählt ist aus boriertem Dispergiermittel, boriertem Dispergiermittel/VI-Verbesserer, Alkalimetall- oder gemischtem Alkalimetall- oder Erdalkalimetallborat, überbasischem boriertem Metalldetergens, boriertem Epoxid und Boratamid.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche in Form einer SAE 10WX- oder SAE 5WX- oder SAE OWX-Ölzusammensetzung, wobei X für jeweils eines von 20, 30 und 40 steht.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, die Salicylat-basiertes Detergens in einer geringeren Menge enthält.
  7. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der Aschegehalt der Zusammensetzung weniger als 1,5 Massen-% beträgt, bezogen auf die Masse der Zusammensetzung, bestimmt gemäß ASTM D-874.
  8. Additivzusammensetzung, die Verdünnungsmittel oder Trägeröl, borhaltiges Additiv und ein oder mehrere Co-Additive in solchen Anteilen umfasst oder durch Mischen derselben hergestellt ist, dass eine Kurbelgehäuseschmierölzusammensetzung mit mehr als 600 ppm Bor, weniger als 200 Massen-ppm Phosphor und weniger als 4000 Massen-ppm Schwefel, bezogen auf die Masse der Zusammensetzung, bereitgestellt wird, wenn die Zusammensetzung 2 bis 20 Massen-% der Additive enthält, wobei die Additivzusammensetzung kein Boratester-Additiv umfasst.
  9. Additivzusammensetzung gemäß Anspruch 8, die ferner eine Detergensadditivzusammensetzung umfasst, die mindestens zwei Detergenzien von mindestens zwei Metallen umfasst.
  10. Verfahren, um einer Schmierölzusammensetzung, die weniger als 200 Massen-ppm Phosphor und weniger als 4000 Massen-ppm Schwefel enthält, bezogen auf das Gewicht der Ölzusammensetzung, Verschleißfestigkeit zu verleihen, indem in der Zusammensetzung borhaltiges Additiv bereitgestellt wird, um mehr als 600 Massen-ppm Bor bereitzustellen, bezogen auf die Masse der Zusammensetzung, wobei die Zusammensetzung kein Boratester-Additiv umfasst.
  11. Verfahren zum Schmieren des Kurbelgehäuses eines Verbrennungsmotors mit Funkenzündung oder Kompressionszündung, bei dem dem Motor eine Schmierölzusammensetzung wie in einem der Ansprüche 1 bis 7 beansprucht zugeführt wird.
  12. Verwendung eines borhaltigen Additivs, das mindestens 600 ppm Bor bereitstellt, in einer Kurbelgehäuseschmierölzusammensetzung, die weniger als 200 Massen-ppm und weniger als 4000 Massen-ppm Schwefel enthält, bezogen auf das Gewicht der Ölzusammensetzung, um Verschleißfestigkeit zu verleihen.
  13. Verwendung eines borhaltigen Additivs, das mindestens 600 ppm Bor bereitstellt, und höchstens 400 Massen-ppm Molybdän aus einem molybdänhaltigen Additiv in einer Schmierölzusammensetzung, die weniger als 200 Massen-ppm Phosphor und weniger 4000 Massen-ppm Schwefel enthält, bezogen auf die Masse der Ölzusammensetzung, um der Ölzusammensetzung Reibungsverminderungs-Leistung und/oder Antioxidansleistung zu verleihen.
EP02257525A 2001-11-09 2002-10-30 Borenthaltende Schmierölzusammensetzung mit niedrigem Schwefel- und Phosphor-Gehalt Expired - Lifetime EP1310549B1 (de)

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EP02250224 2002-01-14
EP02250224A EP1329496A1 (de) 2002-01-14 2002-01-14 Borenthaltende Schmierölzusammensetzung mit niedrigem Schwefel- und Phosphorgehalt
EP02257525A EP1310549B1 (de) 2001-11-09 2002-10-30 Borenthaltende Schmierölzusammensetzung mit niedrigem Schwefel- und Phosphor-Gehalt

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CN1782048B (zh) * 2004-11-30 2011-11-30 英菲诺姆国际有限公司 润滑油组合物
US8513169B2 (en) 2006-07-18 2013-08-20 Infineum International Limited Lubricating oil compositions
US9193931B2 (en) 2008-12-17 2015-11-24 Chevron Oronite Company Llc Lubricating oil compositions
US9303229B2 (en) 2008-12-17 2016-04-05 Chevron U.S.A. Inc. Lubricating oil composition
US9523061B2 (en) 2008-12-17 2016-12-20 Chevron Oronite Company Llc Lubricating oil compositons

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US20040087451A1 (en) * 2002-10-31 2004-05-06 Roby Stephen H. Low-phosphorus lubricating oil composition for extended drain intervals
EP1661970B1 (de) * 2004-11-30 2012-04-04 Infineum International Limited Schmierölzusammensetzungen
US8709988B2 (en) 2004-11-30 2014-04-29 Infineum International Limited Lubricating oil compositions
EP1661969B1 (de) * 2004-11-30 2014-10-08 Infineum International Limited Schmierölzusammensetzungen
US8470751B2 (en) 2005-05-20 2013-06-25 Infineum International Limited Lubricating oil compositions
EP1724329B1 (de) 2005-05-20 2012-10-10 Infineum International Limited Metall-Detergentien-Kombination in Schmierölzusammensetzungen
CN106566596B (zh) 2015-10-08 2021-04-09 英菲诺姆国际有限公司 润滑油组合物

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US4508630A (en) * 1982-01-18 1985-04-02 The Elco Corporation Oil soluble sulfur free oxymolybdenum organic compounds having friction reducing antiwear properties in lubricant compositions, process of manufacture, and lubricant compositions
US4599183A (en) * 1983-09-19 1986-07-08 Mobil Oil Corporation Multifunctional additives
JPH07316577A (ja) * 1994-05-20 1995-12-05 Tonen Corp 潤滑油組成物
CA2195475A1 (en) * 1994-09-01 1996-03-07 Michiya Yamada Lubricants with sustained fuel economy performance
WO1999031113A1 (en) * 1997-12-12 1999-06-24 Infineum Usa L.P. Method for the preparation of trinuclear molybdenum-sulfur compounds and their use as lubricant additives
US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1782048B (zh) * 2004-11-30 2011-11-30 英菲诺姆国际有限公司 润滑油组合物
US8513169B2 (en) 2006-07-18 2013-08-20 Infineum International Limited Lubricating oil compositions
US9193931B2 (en) 2008-12-17 2015-11-24 Chevron Oronite Company Llc Lubricating oil compositions
US9303229B2 (en) 2008-12-17 2016-04-05 Chevron U.S.A. Inc. Lubricating oil composition
US9523061B2 (en) 2008-12-17 2016-12-20 Chevron Oronite Company Llc Lubricating oil compositons

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