EP2290038B1 - Schmierölzusammensetzung - Google Patents

Schmierölzusammensetzung Download PDF

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Publication number
EP2290038B1
EP2290038B1 EP10171307A EP10171307A EP2290038B1 EP 2290038 B1 EP2290038 B1 EP 2290038B1 EP 10171307 A EP10171307 A EP 10171307A EP 10171307 A EP10171307 A EP 10171307A EP 2290038 B1 EP2290038 B1 EP 2290038B1
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EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
mass
lubricant
biodiesel
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.)
Active
Application number
EP10171307A
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English (en)
French (fr)
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EP2290038A2 (de
EP2290038A3 (de
Inventor
Keith Strickland
Stuart James Mctavish
Katherine Richard
Robert Shaw
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
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Infineum International Ltd
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Publication date
Priority claimed from GB0917983A external-priority patent/GB0917983D0/en
Application filed by Infineum International Ltd filed Critical Infineum International Ltd
Priority to EP11169302A priority Critical patent/EP2365049B1/de
Priority to EP10171307A priority patent/EP2290038B1/de
Publication of EP2290038A2 publication Critical patent/EP2290038A2/de
Publication of EP2290038A3 publication Critical patent/EP2290038A3/de
Application granted granted Critical
Publication of EP2290038B1 publication Critical patent/EP2290038B1/de
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—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
    • C10N2030/40—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
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/70—Soluble oils
    • 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
    • C10N2030/78—Fuel contamination
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to automotive lubricating oil compositions, more especially to automotive lubricating oil compositions for use in compression-ignited internal combustion engines fuelled at least in part with a biodiesel fuel, crankcase lubrication, such compositions being referred to as crankcase lubricants.
  • the present invention relates to automotive lubricating oil compositions, preferably having low levels of phosphorus and also low levels of sulfur and/or sulfated ash, that exhibit improved antioxidant properties and/or improved inhibition of the corrosion of the metallic engine parts during operation of the engine which is fuelled with a biofuel; and to the use of additives in such compositions for improving the antioxidant and/or anti-corrosion properties of the lubricating oil composition.
  • a crankcase lubricant is an oil used for general lubrication in an internal combustion engine where an oil sump is situated generally below the crankshaft of the engine and to which circulated oil returns.
  • Biodiesel fuels include components of low volatility which are slow to vaporize after injection of the fuel into the engine. Typically, an unburnt portion of the biodiesel and some of the resulting partially combusted decomposition products become mixed with the lubricant on the cylinder wall and are washed down into the oil sump, thereby contaminating the crankcase lubricant.
  • the biodiesel fuel in the contaminated lubricant may form further decompositions products, due to the extreme conditions during lubrication of the engine. It has been found that the presence of biodiesel fuel and the decomposition products thereof in the crankcase lubricant promotes the corrosion of the metallic engine parts; particularly the softer metallic (i.e.
  • non-ferrous metallic engine parts such as the lead and copper based bearing materials.
  • this problem is significantly worse in diesel engines which employ a late post-injection of fuel into the cylinder (e.g. light duty, medium duty and passenger car diesel engines) to regenerate an exhaust gas after-treatment device.
  • European patent application No. 2141220 A discloses a lubricating oil composition comprising a borated dispersant and an alkaline earth metal detergent for improved detergency in biodiesel applications.
  • European patent application No. 2204438 A discloses a low ash containing lubricating oil composition comprising an alkali metal borate for improved detergency and oxidation stability in biodiesel applications.
  • European patent application No. 2223992 A discloses use of a polyol ester base oil for improved detergency in biofuel applications.
  • United States patent No. 5,739,088 discloses the use of an alkaline earth metal borate in alcohol fuelled engines.
  • European patent application No. 2055 761 A2 discloses a lubricating oil compositions comprising a base oil, and a metal phenate detergent, particularly an alkaline metal phenate, wherein the composition further contains at least 0.3 wt% of a biodiesel fuel or decomposition products thereof.
  • Exhaust gas after-treatment devices such as a diesel particulate filter (DPF)
  • DPF diesel particulate filter
  • One way to create conditions for initiating and sustaining regeneration of a DPF involves elevating the temperature of the exhaust gases entering the DPF to burn the soot. As a diesel engine runs relatively cool and lean, this may be achieved by adding fuel into the exhaust gases optionally in combination with the use of an oxidation catalyst located upstream of the DPF.
  • Heavy duty diesel (HDD) engines such as those in trucks, typically employ a late post-injection of fuel directly into the exhaust system outside of the cylinder, whilst light duty and medium duty diesel engines typically employ a late post-injection of fuel directly into the cylinder during an expansion stroke.
  • the corrosion of the softer metallic (i.e. non-ferrous metallic) engine components increases significantly in a diesel engine fuelled at least in part with biodiesel when the engine employs a late post-injection of fuel directly into the cylinder.
  • this increased engine corrosion is due to more biodiesel being absorbed by the lubricant on the more exposed cylinder wall, thereby increasing contamination of the lubricant in the sump.
  • an alcohol based fuel e.g. bioethanol
  • biofuel particularly biodiesel
  • a biofuel particularly biodiesel
  • piston deposits which may increase the tendency of piston ring-sticking during operation of the engine.
  • lubricating oil compositions which exhibit improved anti-corrosion properties in respect of the metallic engine components, particularly the softer metallic (i.e. non-ferrous metallic) engine components such as those containing copper and/or lead (e.g. bearing materials), need to be identified. Accordingly, lubricants with improved antioxidant properties also need to be identified. Still further, lubricants which exhibit improved piston cleanliness need to be identified.
  • the present invention is based on the discovery that a lubricating oil can be formulated which exhibits significantly improved anti-corrosion properties, particularly in respect of the softer metallic (i.e. non-ferrous metallic) engine components, such as those containing lead and/or copper, and/or improved antioxidant properties and/or improved piston cleanliness.
  • the present invention provides a lubricating oil composition comprising:
  • the lubricating oil composition according to the present invention is a crankcase lubricant.
  • a metal detergent system as claimed in a lubricating oil composition provides a lubricant that exhibits improved inhibition and/or a reduction in the corrosion of the metallic engine components, particularly the softer metallic (i.e. non-ferrous metallic) engine components, in use, in the lubrication of a spark-ignited or compression-ignited internal combustion engine which is fuelled at least in part with a biofuel.
  • a metal detergent system as claimed in a lubricating oil composition improves the antioxidant properties of the lubricant, in use, in the lubrication of an internal combustion engine which is fuelled at least in part with a biofuel.
  • a metal detergent system as claimed in a lubricating oil composition improves the engine piston cleanliness and reduces piston ring-sticking, in use, in the lubrication of an internal combustion engine which is fuelled at least in part with a biofuel.
  • a salicylate detergent system in a lubricant comprising a Group III base stock typically provides, in use, a positive credit in terms of reduced corrosion of the metallic engine components and/or reduced oxidation of the lubricant and/or improved piston cleanliness, whereas the use of a metal sulfonate and/or phenate detergent system typically accelerates metal corrosion and/or oxidation of the lubricant and/or provides inferior engine piston cleanliness.
  • the present invention provides a method of lubricating a compression-ignited internal combustion engine which is fuelled with biodiesel, comprising operating the engine with a lubricating oil composition according to the first aspect of the invention.
  • the method of the second aspect of the present invention reduces and/or inhibits the corrosion of the metallic, particularly the non-ferrous metallic, engine components.
  • the present invention provides the use, in the lubrication of a compression-ignited internal combustion engine which is fuelled with biodiesel, of a lubricating oil composition according to the first aspect of the invention to reduce and/or inhibit the corrosion of the metallic engine components during operation of the engine.
  • the present invention provides the use, in the lubrication of a compression-ignited internal combustion engine which is fuelled with biodiesel, of a metal detergent system according to any one of claims 1 to 4 hereof, as an additive component in a minor amount in a lubricating oil composition, to reduce and/or inhibit the corrosion of the metallic engine components, during operation of the engine wherein the lubricating oil composition becomes contaminated with biodiesel or a decomposition product thereof during operation of the engine.
  • the lubricating oil composition comprises a major amount of an oil of lubricating viscosity comprising a Group III base stock.
  • the metal detergent system comprising one or more metal salicylates includes one or more overbased magnesium salicylates.
  • magnesium salicylates offer performance credits in respect of soft metal corrosion and/or lubricant oxidative stability compared with other metal salicylates.
  • the lubricating oil compositions as defined in the second to fourth aspects of the invention are each independently contaminated with at least 0.3 mass %, based on the total mass of the lubricating oil composition, of a biofuel or a decomposition product thereof and mixtures thereof.
  • the metal detergent system of the present invention forms part of an additive package which also includes a diluent, preferably a base stock, and one or more co-additives in a minor amount, other than additive components (B), selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, antiwear agents, friction modifiers, demulsifiers and antifoam agents; the additive package being added to the oil of lubricating viscosity comprising the Group III base stock.
  • the lubricating oil composition may further include one or more co-additives in a minor amount, other than additive component (B), selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, antifoam agents and viscosity modifiers.
  • additive component (B) selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, antifoam agents and viscosity modifiers.
  • the soft metallic engine components (i.e. non-ferrous metallic) of the metallic engine components of the third and fourth aspects comprise components which include copper or lead and mixtures thereof, especially lead, such as the lead and copper based bearing materials.
  • the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition).
  • a base oil is useful for making concentrates as well as for making lubricating oil compositions therefrom, and may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof.
  • the oil of lubricating viscosity comprises a Group III base stock.
  • the base stock groups are defined in the American Petroleum Institute (API) publication " Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 .
  • the base stock will have a viscosity preferably of 3-12, more preferably 4-10, most preferably 4.5-8, mm 2 /s (cSt) at 100°C.
  • base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication " Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 . Said publication categorizes base stocks as follows:
  • the oil of lubricating viscosity comprises greater than or equal to 10 mass %, more preferably greater than or equal to 20 mass %, even more preferably greater than or equal to 25 mass %, even more preferably greater than or equal to 30 mass %, even more preferably greater than or equal to 40 mass %, even more preferably greater than or equal to 45 mass % of a Group III base stock, based on the total mass of the oil of lubricating viscosity.
  • the oil of lubricating viscosity comprises greater than 50 mass %, preferably greater than or equal to 60 mass %, more preferably greater than or equal to 70 mass %, even more preferably greater than or equal to 80 mass %, even more preferably greater than or equal to 90 mass % of a Group III base stock, based on the total mass of the oil of lubricating viscosity.
  • the oil of lubricating viscosity consists essentially of a Group III base stock.
  • the Group III base stock may be the sole oil of lubricating viscosity in the lubricating oil composition.
  • Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybut
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dim
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Unrefined, refined and re-refined oils can be used in the compositions of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.
  • base oil examples include gas-to-liquid (“GTL”) base oils, i.e. the base oil may be an oil derived from Fischer-Tropsch synthesised hydrocarbons made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • GTL gas-to-liquid
  • the oil of lubricating viscosity may also comprise a Group I, Group II, Group IV or Group V base stocks or base oil blends of the aforementioned base stocks.
  • the volatility of the oil of lubricating viscosity or oil blend is less than or equal to 16%, preferably less than or equal to 13.5%, preferably less than or equal to 12%, more preferably less than or equal to 10%, most preferably less than or equal to 8%.
  • the viscosity index (VI) of the oil of lubricating viscosity is at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, most preferably from about 130 to 140.
  • the oil of lubricating viscosity is provided in a major amount, in combination with a minor amount of additive component (B), as defined herein and, if necessary, one or more co-additives, such as described hereinafter, constituting a lubricating oil composition.
  • additive component (B) as defined herein and, if necessary, one or more co-additives, such as described hereinafter, constituting a lubricating oil composition.
  • This preparation may be accomplished by adding the additives directly to the oil or by adding them in the form of a concentrate thereof to disperse or dissolve the additive.
  • Additives may be added to the oil by any method known to those skilled in the art, either before, at the same time as, or after addition of other additives.
  • the oil of lubricating viscosity is present in an amount of greater than 55 mass %, more preferably greater than 60 mass %, even more preferably greater than 65 mass %, based on the total mass of the lubricating oil composition.
  • the oil of lubricating viscosity is present in an amount of less than 98 mass %, more preferably less than 95 mass %, even more preferably less than 90 mass %, based on the total mass of the lubricating oil composition.
  • the lubricating oil compositions of the invention comprise defined components that may or may not remain the same chemically before and after mixing with an oleaginous carrier.
  • This invention encompasses compositions which comprise the defined components before mixing, or after mixing, or both before and after mixing.
  • concentrates When concentrates are used to make the lubricating oil compositions, they may for example be diluted with 3 to 100, e.g. 5 to 40, parts by mass of oil of lubricating viscosity per part by mass of the concentrate.
  • the lubricating oil composition of the present invention contains low levels of phosphorus, namely up to 0.12 mass %, preferably up to 0.11 mass %, more preferably not greater than 0.10 mass %, even more preferably up to 0.09 mass %, even more preferably up to 0.08 mass %, even more preferably up to 0.06 mass % of phosphorus, expressed as atoms of phosphorus, based on the total mass of the composition.
  • the lubricating oil composition may contain low levels of sulfur.
  • the lubricating oil composition contains up to 0.4, more preferably up to 0.3, most preferably up to 0.2, mass % sulfur, expressed as atoms of sulfur, based on the total mass of the composition.
  • the lubricating oil composition may contain low levels of sulphated ash.
  • the lubricating oil composition contains up to and including 1.2, more preferably up to 1.1, even more preferably up to 1.0, even more preferably up to 0.8, mass % sulphated ash, based on the total mass of the composition.
  • the lubricating oil composition is a multigrade identified by the viscometric descriptor SAE 20WX, 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.
  • Metal detergents are additives that reduce formation of piston deposits in engines and that may have acid-neutralising properties, and the term 'detergent' is used herein to define a material capable of providing either or both of these functions within the lubricating oil composition. They are based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants, and that generally comprise a polar head with a long hydrophobic tail. Large amounts of a metal base can be included by reacting an excess of a metal base, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • a metal base such as an oxide or hydroxide
  • the metal detergent system (B) comprises one or more oil soluble overbased alkaline earth metal salicylates i.e. one or more metal salts ofsalicylic acids, including one or more oil soluble overbased magnesium salicylates.
  • Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol.
  • Salicylic acids may be non-sulphurized or sulphurized, and may be chemically modified and/or contain additional substituents. Processes for sulphurizing a hydrocarbyl-substituted salicylic acid are well known to those skilled in the art, and are described, for example, in US 2007/0027057 .
  • the salicylic acids are non-sulphurized.
  • the one or more metal salicylates comprise one or more hydrocarbyl-substituted salicylates, namely the surfactant of the soap comprises one or more hydrocarbyl-substituted salicylic acids.
  • each surfactant moiety of the soap comprises a hydrocarbyl-substituted salicylic acid, more preferably each surfactant moiety comprises an alkyl substituted salicylic acid, most preferably each surfactant moiety independently represents a C 8 to C 30 alkyl substituted salicylic acid.
  • alkyl groups include: octyl, nonyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, docosyl, tricosyl, hexacosyl, triacontyl, dimethylcyclohexyl, ethylcyclohexyl, methylcyclohexylmethyl and cyclohexylethyl.
  • the alkaline earth metal of the one or more alkaline earth metal salicylates is e.g. calcium, magnesium, barium or strontium. More preferably, the alkaline earth metal is calcium or magnesium.
  • the lubricating oil composition comprises a combination of one or more calcium salicylates and one or more magnesium salicylates, preferably one or more overbased calcium salicylates and one or more overbased magnesium salicylates.
  • the salts may contain a substantially stoichiometric amount of the metal when they are usually described as normal or neutral salts and would typically have a total base number or TBN (as may be measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Large amounts of a metal base can be included by reaction of an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralised detergent as an outer layer of a metal base (e.g. carbonate) micelle.
  • Such overbased detergents may have a TBN of 100 or greater, and typically of from 250 to 500.
  • the metal detergent system comprises one or more overbased calcium salicylate.
  • the metal detergent system may contain two or more different metal detergents of the same surfactant, for example an alkali metal salicylate and an alkaline earth metal salicylate, or a magnesium salicylate and a calcium salicylate.
  • the metal detergent system may also contain two or more different detergents having a different surfactant type, for example one or more metal salicylates plus one or more metal sulphonates and/or metal phenates.
  • Metal detergent systems including two or more different detergents having a different surfactant type include "hybrid” detergents formed with mixed surfactant systems, e.g., phenate/salicylates (sometimes referred to as "phenalates"), sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Patent Nos. 6,153,565 ; 6,281,179 ; 6,429,178 ; and 6,429,179 .
  • the lubricating composition may include other metal detergents apart from the metal salicylate, for example metal phenate detergents, preferably the one or more metal salicylates is the predominant metal detergent in the lubricating oil composition.
  • the one or more metal salicylates contribute greater than 50 %, preferably greater than 60 %, more preferably greater than 70 %, even more preferably greater than 80 %, most preferably greater than 90 %, of the total TBN from all of the ash forming metal detergents in the lubricating composition.
  • the one or more metal salicylates is essentially the sole metal detergent of the metal detergent system in the lubricating oil composition.
  • the lubricating composition includes a metal detergent system from which metal phenates and metal sulfonates are substantially, or more preferably completely, absent.
  • the metal detergent system of the lubricating oil composition is used in amounts which provide the lubricating oil composition with a TBN of from about 4 to 15, preferably 5 to 12.
  • TBN of the lubricating composition ranges from about 4 to 12, such as 6 to 12, preferably from about 7 to 12.
  • a detergent is generally added in amounts that provide the lubricating oil composition with a TBN of from about 5.0 to about 12.0, such as from about 5.0 to about 11.0.
  • the metal detergent system is used in an amount which introduces at least about 6 mmols, preferably at least 9 mmols, more preferably at least 15 mmols, such as at least about 18 mmols, even more preferably at least 20 mmols, even more preferably at least about 24 mmols, of soap (i.e. salicylate) per kilogram of finished lubricant.
  • soap i.e. salicylate
  • the one or more oil soluble overbased alkaline earth metal salicylates provide from 50 to 4,000 preferably from 100 to 3,000, ppm by mass of atoms of metal, based on the mass of the lubricating oil composition.
  • the lubricating oil compositions of the invention may be used to lubricate mechanical engine components, particularly in internal combustion engines, e.g. spark-ignited or compression-ignited two- or four- stroke reciprocating engines, by adding the composition thereto.
  • the engines may be conventional gasoline or diesel engines designed to be powered by gasoline or petroleum diesel, respectively; alternatively, the engines may be specifically modified to be powered by an alcohol based fuel or biodiesel fuel.
  • the lubricating oil compositions are crankcase lubricants.
  • the lubricating oil composition is for use in the lubrication of a compression-ignited internal combustion engine (diesel engine), especially a compression-ignited internal combustion engine which is fuelled at least in part with a biodiesel fuel.
  • a compression-ignited internal combustion engine diesel engine
  • Such engines include passenger car diesel engines and heavy duty diesel engines, for example engines found in road trucks.
  • the lubricating oil composition is for use in the lubrication of a passenger car compression-ignited internal combustion engine (i.e. a light duty diesel engine), which is fuelled at least in part with a biodiesel fuel, especially such an engine which employs a late post-injection of fuel into the cylinder.
  • the lubricating oil composition is for use in the lubrication of the crankcase of the aforementioned engines.
  • the lubricating oil composition such as a crankcase lubricant
  • the lubricating oil composition of the present invention comprises at least 0.3, preferably at least 0.5, more preferably at least 1, even more preferably at least 5, even more preferably at least 10, even more preferably at least 15, even more preferably at least 20, mass % of biofuel and/or a decomposition product thereof.
  • the lubricating oil composition may comprise up to 50 mass % of biofuel and/or a decomposition product thereof, preferably it includes less than 35, more preferably less than 30, mass % of biofuel and/or a decomposition product thereof.
  • the biofuel comprises an alcohol based fuel in the case of spark-ignited internal combustion engines, preferably a bioalcohol fuel, especially bioethanol fuel.
  • the biofuel comprises biodiesel in the case of compression ignited internal combustion engines.
  • Biofuels include fuels that are produced from renewable biological resources and include biodiesel fuel as defined herein and bioethanol fuel which may be derived from fermented sugar.
  • biofuel also embraces an "alcohol based fuel”, such as “ethanol based fuel”, irrespective of the source of the alcohol (i.e. the alcohol may be derived from a renewable biological source or a non-renewable source, such as petroleum).
  • Alcohol based fuels are employed in spark-ignited internal combustion engines.
  • the alcohol based fuel may include one or more alcohols selected from methanol, ethanol, propanol and butanol.
  • the alcohol may be derived from a renewable biological source or a non-renewable source, such as petroleum.
  • the alcohol based fuel may comprise 100 % by volume of one or more alcohols (i.e. pure alcohol).
  • the alcohol based fuel may comprise a blend of an alcohol and petroleum gasoline; suitable blends include 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80, 85, and 90, vol.% of the alcohol, based on the total volume of the alcohol and gasoline blend.
  • the alcohol based fuel comprises an ethanol based fuel. More preferably, the alcohol based fuel comprises a bioalcohol fuel, especially a bioethanol fuel.
  • the bioethanol fuel comprises ethanol derived from a renewable biological source (i.e. bioethanol), preferably ethanol derived solely from a renewable biological source.
  • the bioethanol may be derived from the sugar fermentation of crops such as corn, maize, wheat, cord grass and sorghum plants.
  • the bioethanol fuel may comprise 100% by volume bioethanol (designated as E100); alternatively, the bioethanol fuel may comprise a blend of bioethanol and petroleum gasoline.
  • the bioethanol fuel blend may have the designation "Exx" wherein xx refers to the amount of E100 bioethanol in vol.%, based on the total volume of the bioethanol fuel blend.
  • E10 refers to a bioethanol fuel blend which comprises 10 volume % E100 bioethanol fuel and 90 volume % of petroleum gasoline.
  • bioethanol fuel includes pure bioethanol fuel (i.e. E100) and bioethanol fuel blends comprising a mixture of bioethanol fuel and petroleum gasoline fuel.
  • the bioethanol fuel comprises E100, E95, E90, E85, E80, E75, E70, E65, E60, E55, E50, E45, E40, E35, E30, E25, E20, E15, E10, E8, E6 or E5.
  • Highly preferred blends include E85 (ASTM D5798 (USA)), E10 (ASTM D4806 (USA)) and E5 (EN 228:2004 (Europe)).
  • the biodiesel fuel comprises at least one alkyl ester, typically a mono-alkyl ester, of a long chain fatty acid derivable from vegetable oils or animal fats.
  • the biodiesel fuel comprises one or more methyl or ethyl esters of such long chain fatty acids, especially one or more methyl esters.
  • the long chain fatty acids typically comprise long chains which include carbon, hydrogen and oxygen atoms.
  • the long chain fatty acids include from 10 to 30, more preferably 14 to 26, most preferably 16 to 22, carbon atoms.
  • Highly preferred fatty acids include palmitic acid, stearic acid, oleic acid and linoleic acid.
  • the biodiesel fuel may be derived from the esterification or transesterification of one or more vegetable oils and animal fats, such as corn oil, cashew oil, oat oil, lupine oil, kenaf oil, calendula oil, cotton oil, hemp oil, soybean oil, linseed oil, hazelnut oil, euphorbia oil, pumpkin seed oil, palm oil, rapeseed oil, olive oil, tallow oil, sunflower oil, rice oil, sesame oil or algae oil.
  • Preferred vegetable oils include palm oil, rapeseed oil and soybean oil.
  • a pure biodiesel fuel that meets the ASTM D6751-08 standard (USA) or EN 14214 standard (European) specifications is designated as B100.
  • a pure biodiesel fuel may be mixed with a petroleum diesel fuel to form a biodiesel blend which may reduce emissions and improve engine performance.
  • Such biodiesel blends are given a designation "Bxx" where xx refers to the amount of the B100 biodiesel in volume %, based on the total volume of the biodiesel blend.
  • B10 refers to a biodiesel blend which comprises 10 volume % B100 biodiesel fuel and 90 volume % of petroleum diesel fuel.
  • biodiesel fuel includes pure biodiesel fuel (i.e. B100) and biodiesel fuel blends comprising a mixture of biodiesel fuel and petroleum diesel fuel.
  • the biodiesel fuel comprises a B100, B95, B90, B85, B80, B75, B70, B65, B60, B55, B50, B45, B40, B35, B30, B25, B20, B15, B10, B8, B6, B5, B4, B3, B2 or B1.
  • the biodiesel fuel comprises a B50 designation or lower, more preferably a B5 to B40, even more preferably B5 to B40, most preferably B5 to B20.
  • Co-additives with representative effective amounts, that may also be present, different from additive component (B), are listed below. All the values listed are stated as mass percent active ingredient.
  • Ashless Dispersant 0.1 - 20 1 - 8 Metal Detergents 0.1 - 15 0.2 - 9 Friction modifier 0 - 5 0 - 1.5 Corrosion Inhibitor 0 - 5 0 - 1.5 Metal Dihydrocarbyl Dithiophosphate 0 - 10 0 - 4 Anti-Oxidants 0 - 5 0.01 - 3 Pour Point Depressant 0.01 - 5 0.01 - 1.5 Anti-Foaming Agent 0 - 5 0.001 - 0.13 Supplement Anti-Wear Agents 0 - 5 0 - 2 Viscosity Modifier (1) 0 - 6 0.01 - 4 Mineral or Synthetic Base Oil Balance Balance (1) Viscosity modifiers are used only in multi-graded oils.
  • the final lubricating oil composition typically made by blending the or each additive into the base oil, may contain from 5 to 25, preferably 5 to 18, typically 7 to 15, mass % of the co-additives, the remainder being oil of lubricating viscosity.
  • additives can provide a multiplicity of effects, for example, a single additive may act as a dispersant and as an oxidation inhibitor.
  • a dispersant is an additive whose primary function is to hold solid and liquid contaminations in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Dispersants are usually "ashless", as mentioned above, being non-metallic organic materials that form substantially no ash on combustion, in contrast to metal-containing, and hence ash-forming materials. They comprise a long hydrocarbon chain with a polar head, the polarity being derived from inclusion of e.g. an O, P, or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric backbone.
  • a preferred class of olefin polymers is constituted by polybutenes, specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • PIB polyisobutenes
  • poly-n-butenes such as may be prepared by polymerization of a C 4 refinery stream.
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • a noteworthy group of dispersants is constituted by hydrocarbon-substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine.
  • reaction products of polyalkylene polyamines with alkenyl succinic anhydrides such as described in US-A-3,202,678 ; - 3,154,560 ; - 3,172,892 ; - 3,024,195 ; - 3,024,237 , - 3,219,666 ; and - 3,216,936 , that may be post-treated to improve their properties, such as borated (as described in US-A-3,087,936 and - 3,254,025 ) fluorinated and oxylated.
  • boration may be accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
  • the lubricating oil composition includes an oil-soluble boron containing compound, especially a borated dispersant.
  • the borated dispersant comprises an ashless nitrogen containing borated dispersant, such as a borated polyalkenyl succinimide, especially a borated polyisobutenyl succinimide.
  • a detergent in addition to additive component B, may be present in the lubricating oil compositions.
  • Detergents which may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, calcium and magnesium.
  • the most commonly-used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • the detergent system comprising one or more metal salicylates is the sole detergent in the lubricating oil composition.
  • Friction modifiers include glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine.
  • Other known friction modifiers comprise oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition. Suitable oil-soluble organo-molybdenum compounds have a molybdenum-sulfur core. As examples there may be mentioned dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates. The molybdenum compound is dinuclear or trinuclear.
  • One class of preferred organo-molybdenum compounds useful in all aspects of the present invention is tri-nuclear molybdenum compounds of the formula Mo 3 S k L n Q z and mixtures thereof wherein L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compounds soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 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 molybdenum compounds may be present in a lubricating oil composition at a concentration in the range 0.1 to 2 mass %, or providing at least 10 such as 50 to 2,000 ppm by mass of molybdenum atoms.
  • the molybdenum from the molybdenum compound is present in an amount of from 10 to 1500, such as 20 to 1000, more preferably 30 to 750, ppm based on the total weight of the lubricating oil composition.
  • the molybdenum is present in an amount of greater than 500 ppm.
  • Anti-oxidants are sometimes referred to as oxidation inhibitors; they increase the resistance of the composition to oxidation and may work by combining with and modifying peroxides to render them harmless, by decomposing peroxides, or by rendering an oxidation catalyst inert. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • radical scavengers e.g. sterically hindered phenols, secondary aromatic amines, and organo-copper salts
  • hydroperoxide decomposers e.g., organosulfur and organophosphorus additives
  • multifunctionals e.g. zinc dihydrocarbyl dithiophosphates, which may also function as anti-wear additives, and organo-molybdenum compounds, which may also function as friction modifiers and anti-wear additives).
  • suitable antioxidants are selected from copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine-containing antioxidants, hindered phenolic antioxidants, dithiophosphates derivatives, metal thiocarbamates, and molybdenum-containing compounds.
  • Preferred anti-oxidants are aromatic amine-containing antioxidants, molybdenum-containing compounds and mixtures thereof, particularly aromatic amine-containing antioxidants.
  • an antioxidant is present in the lubricating oil composition.
  • Anti-wear agents reduce friction and excessive wear and are usually based on compounds containing sulfur or phosphorous or both, for example that are capable of depositing polysulfide films on the surfaces involved.
  • dihydrocarbyl dithiophosphate metal salts wherein the metal may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel, copper, or preferably, zinc.
  • the lubricating oil composition includes a dihydrocarbyl dithiophosphate metal salt as defined herein.
  • Dihydrocarbyl dithiophosphate metal salts may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a metal compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral metal compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of metal due to the use of an excess of the basic metal compound in the neutralization reaction.
  • the preferred dihydrocarbyl dithiophosphate metal salts are zinc dihydrocarbyl dithiophosphates (ZDDP) which are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein R 1 and R 2 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and include radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R 1 and R 2 groups are alkyl groups of 2 to 8 carbon atoms, especially primary alkyl groups (i.e. R 1 and R 2 are derived from predominantly primary alcohols).
  • ZDDP zinc dihydrocarbyl dithiophosphates
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, iso-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. R 1 and R 2 ) in the dithiophosphoric acid will generally be about 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate comprises a zinc dialkyl dithiophosphate.
  • the lubricating oil composition contains an amount of dihydrocarbyl dithiophosphate metal salt that introduces 0.02 to 0.10 mass %, preferably 0.02 to 0.09 mass%, preferably 0.02 to 0.08 mass %, more preferably 0.02 to 0.06 mass % of phosphorus into the composition.
  • the dihydrocarbyl dithiophosphate metal salt should preferably be added to the lubricating oil compositions in amounts no greater than from 1.1 to 1.3 mass % (a.i.), based upon the total mass of the lubricating oil composition.
  • ashless anti-wear agents examples include 1,2,3-triazoles, benzotriazoles, sulfurised fatty acid esters, and dithiocarbamate derivatives.
  • Rust and corrosion inhibitors serve to protect surfaces against rust and/or corrosion.
  • rust inhibitors there may be mentioned non-ionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles and anionic alkyl sulfonic acids.
  • Pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the oil will flow or can be poured.
  • Such additives are well known. Typical of these additive are C 8 to C 18 dialkyl fumerate/vinyl acetate copolymers and polyalkylmethacrylates.
  • Additives of the polysiloxane type for example silicone oil or polydimethyl siloxane, can provide foam control .
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is described in EP-A-330,522 . It is obtained by reacting an alkylene oxide with an adduct obtained by reaction of a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient is convenient.
  • Viscosity modifiers impart high and low temperature operability to a lubricating oil.
  • Viscosity modifiers that also function as dispersants are also known and may be prepared as described above for ashless dispersants.
  • these dispersant viscosity modifiers are functionalised polymers (e.g. interpolymers of ethylene-propylene post grafted with an active monomer such as maleic anhydride) which are then derivatised with, for example, an alcohol or amine.
  • the lubricant may be formulated with or without a conventional viscosity modifier and with or without a dispersant viscosity modifier.
  • Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters.
  • Oil-soluble viscosity modifying polymers generally have weight average molecular weights of from 10,000 to 1,000,000, preferably 20,000 to 500,000, which may be determined by gel permeation chromatography or by light scattering.
  • the additives may be incorporated into an oil of lubricating viscosity (also known as a base oil) in any convenient way.
  • each 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.
  • an additive is available as an admixture with a base oil so that the handling thereof is easier.
  • additives When a plurality of additives are employed it may be desirable, although not essential, to prepare one or more additive packages (also known as additive compositions or concentrates) comprising additives and a diluent, which can be a base oil, whereby the 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 oil of lubricating viscosity may be facilitated by diluent or solvents and by mixing accompanied with mild heating, but this is not essential.
  • additive packages also known as additive compositions or concentrates
  • a diluent which can be a base oil
  • dissolution of the additive package(s) into the oil of lubricating viscosity may be facilitated by diluent or 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 oil of lubricating viscosity.
  • one or more detergents may be added to small amounts of base oil or other compatible solvents (such as a carrier oil or diluent oil) together with other desirable additives to form additive packages containing from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass %, based on the mass of the additive package, of additives on an active ingredient basis in the appropriate proportions.
  • the final formulations may typically contain 5 to 40 mass % of the additive package(s), the remainder being oil of lubricating viscosity.
  • the metal detergent system comprising one or more metal salicylates (i.e. additive component (B)) forms part of an additive package which also includes a diluent, preferably a base stock, and one or more co-additives in a minor amount, other than additive component (B), selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, antiwear agents, friction modifiers, demulsifiers and antifoam agents; the additive package being added to the oil of lubricating viscosity comprising a Group III base stock.
  • additive component (B) forms part of an additive package which also includes a diluent, preferably a base stock, and one or more co-additives in a minor amount, other than additive component (B), selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, antiwear agents, friction modifiers, demulsifiers and antifoam agents; the additive package being added to the oil of lubricating viscosity comprising a Group III base
  • HTCBT High Temperature Corrosion Bench Test
  • test lubricating oil 100 ml
  • the sample tube is immersed in a heated oil bath so that the temperature of the test lubricating oil is heated to 135°C.
  • the test lubricating oil is heated at 135°C for 168 hours and during this time dry air is blown through the heated oil at a rate of 5 litres per hour. After which, the test lubricating oil is cooled and the metal specimens removed and examined for corrosion.
  • concentration of copper, tin and lead in the test lubricating oil composition and a reference sample of the lubricating oil composition i.e.
  • test lubricating oil a new sample of the test lubricating oil is then determined in accordance with ASTM D5185.
  • concentration of each of the metal contaminants in the test lubricating oil composition and those of the reference sample lubricating oil composition provides a value for the change in the various metal concentrations before and after the test.
  • the industry standard limits to meet the requirements of API CJ-4 which involves testing the lubricant in the absence of any added fuel, are 20 ppm maximum for copper and 120 ppm maximum for lead (i.e. these are the test limits for the pure lubricant only).
  • a lubricating oil composition which includes a biofuel or a petroleum fuel
  • the test has essentially been modified and such compositions are not required to meet the requirements of API CJ-4; the results of the test being used for comparative purposes to assess the effects of certain additives in the presence of a biofuel.
  • Oxidative stability is measured using the Hot Surface Oxidation Test which determines the Oxidation Induction Time (OIT) of a lubricating oil composition by Pressure Differential Scanning Calorimetry (PDSC).
  • OIT Oxidation Induction Time
  • a measured sample (3 mg) of a lubricating oil composition is placed in a test cell of a Pressure Differential Scanning Calorimeter (Netzsch 204 HPDSC) and the cell pressurised to 689.5 KPa (100 psi) with clean dry air. The cell is then heated at a rate of 40°C per minute until the isothermal test temperature of 210°C is attained and the sample maintained at this temperature for a maximum of 240 minutes.
  • the calorimeter provides a value of the OIT i.e. the time taken for the sample to oxidise; a larger OIT indicates the sample is more stable to oxidation than a sample having a smaller OIT.
  • the deposit forming tendency of a lubricating oil composition under temperature and environmental conditions as being significant in internal combustion engines is measured using the TEOST MHT-4 Test in accordance with ASTM D7097, and modified accordingly by the addition of biofuel to the lubricant where appropriate.
  • a sample of the lubricating oil composition including a biofuel where appropriate, is placed in the TEOST test apparatus (available from Tannas, Midland MI, USA) along with a proprietary catalyst (0.01g of catalyst per 1g of lubricant, available from Tannas).
  • the lubricant is then cycled down (approximately 0.25 g/min) the outside of a pre-weighed depositor rod, which is resistively heated to a constant temperature of 285°C in a mantle chamber, for 24 hours. During this time dry air is forced to flow through the mantle chamber at a rate of 10 ml/min.
  • the depositor rod is removed from the mantle chamber and soaked in cyclohexane (3 x 300 ml).
  • the cyclohexane is filtered and any deposits collected and weighed.
  • the total mass of deposits (in mg) formed is determined by weighing the mass of the rod to determine the mass of deposits remaining on the rod and adding this to the mass of deposits collected by filtration. A lower total mass of deposits formed is indicative of improved piston cleanliness.
  • a series of 5W-30 multigrade lubricating oil compositions were prepared by admixing an identical Group III base stock with known additives including a detergent selected from an overbased calcium salicylate detergent (TBN 217) or a mixture of an overbased calcium sulphonate detergent (TBN 300) and an overbased calcium phenate detergent (TBN 140), a dispersant, ZDDP, an aminic antioxidant, a phenolic antioxidant and a viscosity modifier concentrate. All additives described herein are available as standard from lubricant additive companies such as Infineum UK Ltd, Lubrizol Corporation, Afton Chemicals Corp, for example.
  • Reference Lubricants 1 and 2 did not include any biodiesel fuel (i.e. the lubricants per se ), whereas Lubricant 1 and Lubricant 2 included 5 mass % B50 biodiesel fuel (i.e. 5 mass % of a fuel comprising B100 biodiesel fuel (50 mass %) and petroleum diesel fuel (50 mass %)) to simulate contamination of the oil during operation of a diesel engine fuelled with a biodiesel fuel.
  • Reference Lubricant 1 and Lubricant 1 included the overbased calcium salicylate detergent
  • Reference Lubricant 2 and Lubricant 2 included a comparable amount of the overbased calcium sulphonate detergent and calcium phenate detergent.
  • Lubricant 1 and Lubricant 2 had a phosphorus content of 0.2 mass %, a sulphated ash content of 1 mass % and a TBN of 8.85. each of the Lubricants were evaluated for copper and lead corrosion control using the High Temperature Corrosion Bench Test. The results are detailed in Table 1 below. Table 1.
  • Two 5W-30 multigrade lubricating oil compositions (Lubricant 3 and Lubricant 4), as detailed in Table 2, were prepared by admixing an identical Group III base stock with known additives including a detergent selected from an overbased calcium salicylate detergent (TBN 217) or a mixture of an overbased calcium sulphonate detergent (TBN 300) and an overbased calcium phenate detergent (TBN 140), a dispersant, an organo-molybdenum dithiocarbamate compound, ZDDP, an aminic antioxidant, a hindered phenol ester antioxidant and a viscosity modifier concentrate.
  • a detergent selected from an overbased calcium salicylate detergent (TBN 217) or a mixture of an overbased calcium sulphonate detergent (TBN 300) and an overbased calcium phenate detergent (TBN 140), a dispersant, an organo-molybdenum dithiocarbamate compound, ZDDP, an aminic antioxidant, a hindered phenol ester antioxidant and a
  • Lubricant 3 included the overbased calcium salicylate detergent, whereas Lubricant 4 included a comparable amount of the overbased calcium sulphonate detergent and a calcium phenate detergent. Both of the lubricants had a phosphorus content of 0.08 mass %, a sulphated ash content of 0.83 mass % and a TBN of 7.85.
  • B50 biodiesel fuel i.e. 5 mass % of a fuel comprising B100 biodiesel fuel (50 mass %) and petroleum diesel fuel (50 mass %) was added to both of the lubricants to simulate contamination of the oil during operation of a diesel engine fuelled with a biodiesel fuel. The oxidative stability of each lubricant was determined using the Hot Surface Oxidation Test. The results are also detailed in Table 2.
  • a series of 5W-30 multigrade lubricating oil compositions were prepared by admixing an identical Group III base stock with known additives including a detergent selected from an overbased calcium salicylate detergent (TBN 217) or an overbased calcium sulphonate detergent (TBN 300) plus a neutral calcium sulphonate detergent (TBN 17) or an overbased calcium phenate detergent (TBN 250), a dispersant, a ZDDP, an aminic antioxidant and a viscosity modifier concentrate.
  • a detergent selected from an overbased calcium salicylate detergent (TBN 217) or an overbased calcium sulphonate detergent (TBN 300) plus a neutral calcium sulphonate detergent (TBN 17) or an overbased calcium phenate detergent (TBN 250)
  • a dispersant a ZDDP, an aminic antioxidant and a viscosity modifier concentrate.
  • Lubricants 6 and 9 included the overbased calcium sulphonate detergent plus a neutral calcium sulphonate detergent; Lubricants 7 and 10 included the overbased calcium phenate detergent; whereas, Lubricants 5 and 8 included the overbased calcium salicylate detergent.
  • 10 mass % B50 biodiesel fuel i.e. 5 mass % of a fuel comprising B100 biodiesel fuel (50 mass %) and petroleum diesel fuel (50 mass %) was added to each of the lubricants to simulate contamination of the oil during operation of a diesel engine fuelled with a biodiesel fuel.
  • a lubricant comprising a salicylate detergent exhibits improved copper and lead corrosion control performance, in the presence of a biofuel, compared with a comparable lubricant, having the same level of soap and TBN, including a sulphonate detergent or a phenate detergent (compare Lubricant 5 with Lubricants 6 and 7 or compare Lubricant 8 with Lubricants 9 and 10).
  • a lubricant comprising a salicylate detergent exhibits reduced deposit formation (i.e. indicative of enhanced piston cleanliness), in the presence of a biofuel, compared with a comparable lubricant, having the same level of soap and TBN, including a sulphonate detergent or a phenate detergent (compare Lubricant 5 with Lubricants 6 and 7).
  • a lubricant comprising a salicylate detergent is more stable to oxidation, in the presence of a biofuel, compared with a comparable lubricant, having the same level of soap and TBN including a sulphonate detergent or a phenate detergent (compare oxidation induction time (OIT) of Lubricant 5 with Lubricant 6 and Lubricant 7).
  • OIT oxidation induction time
  • Lubricant 6 or Lubricant 7 does not significantly increase the oxidation stability of the resulting lubricants in the presence of a biofuel.
  • Table 3 Lubricant 5 (wt %) Lubricant 6 (wt %) Lubricant 7 (wt %) Lubricant 8 (wt %) Lubricant 9 (wt %) Lubricant 10 (wt %) Ca salicylate detergent 2.5 0 0 3.75 0 0 Ca sulphonate detergent (TBN 300) 0 1.73 0 0 2.60 0 Ca sulphonate detergent (TBN 17) 0 2.66 0 0 3.99 0 Ca phenate detergent 0 0 2.17 0 0 3.26 Dispersant 5.5 5.5 5.5 5.5 5.5 ZDDP 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Viscosity modifier concentrate 5.5 5.5 5.5 5.5 5.5 5.5 ZDDP 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Viscosity modifier
  • a series of 5W-30 multigrade lubricating oil compositions (Lubricant 11 of the invention and Lubricants 12 and 13), as detailed in Table 4, were prepared by admixing an identical Group III base stock with known additives including a detergent selected from a mixture of overbased calcium salicylate detergents (TBN 217 and TBN of 335) or an overbased magnesium salicylate detergent (TBN 340), a dispersant, a ZDDP, an aminic antioxidant and a viscosity modifier concentrate. 10 mass % B50 biodiesel fuel (i.e.
  • a lubricant including a magnesium salicylate detergent exhibits essentially the same copper corrosion control performance, in the presence of a biofuel, as a comparable lubricant including a calcium salicylate detergent, having the same level of soap, TBN and/or sulphated ash (compare Lubricant 11 with Lubricant 12 and also Lubricant 11 with Lubricant 13).
  • a lubricant including a magnesium salicylate detergent exhibits far superior lead corrosion control performance, in the presence of a biofuel, compared to a comparable lubricant including a calcium salicylate detergent, having the same level of soap, TBN and/or sulphated ash (compare Lubricant 11 with Lubricant 12 and also Lubricant 11 with Lubricant 13).
  • a lubricant including a magnesium salicylate detergent is more stable to oxidation, in the presence of a biofuel, than a comparable lubricant including a calcium salicylate detergent, having the same level of soap, TBN and/or sulphated ash (compare Lubricant 11 with Lubricant 12 and also Lubricant 11 with Lubricant 13).

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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. Schmierölzusammensetzung, die:
    (A) in einer größeren Menge Öl mit Schmierviskosität, das Basismaterial aus Gruppe III umfasst,
    (B) in einer geringeren Menge ein Metalldetergenzsystem als Additivbestandteil umfasst, das ein oder mehrere öllöslichen überbasische Erdalkalimetallsalicylate umfasst, die ein oder mehrere öllösliche überbasische Magnesiumsalicylate umfassen, und
    wobei die Schmierölzusammensetzung mit mindestens 0,3 Masse-%, bezogen auf die gesamte Masse der Schmierölzusammensetzung, Biodiesel oder eines Zersetzungsprodukts davon kontaminiert ist und wobei das eine oder die mehreren öllöslichen Erdalkalimetallsalicylate von 50 bis 4000 Masse-ppm Metallatome zur Verfügung stellen, bezogen auf die Masse der Schmierölzusammensetzung.
  2. Schmierölzusammensetzung wie in Anspruch 1 beansprucht, wobei das Metalldetergenzsystem eine Kombination des einen oder der mehreren öllöslichen überbasischen Magnesiumsalicylate und des einen oder der mehreren öllöslichen überbasischen Calciumsalicylate umfasst.
  3. Schmierölzusammensetzung wie in Anspruch 1 oder Anspruch 2 beansprucht, wobei das Metalldetergenzsystem im Wesentlichen aus dem einen oder den mehreren öllöslichen überbasischen Erdalkalimetallsalicylaten besteht.
  4. Schmierölzusammensetzung wie in einem der vorhergehenden Ansprüche beansprucht, wobei das eine oder die mehreren öllöslichen überbasischen Erdalkalimetallsalicylate mindestens 6 mmol Seife pro Kilogramm fertiges Schmiermittel einbringen.
  5. Schmierölzusammensetzung wie in einem der vorhergehenden Ansprüche beansprucht, wobei die Zusammensetzung eine Phosphorkonzentration von nicht größer als 0,10 Masse-% aufweist, ausgedrückt als Phosphoratome.
  6. Schmierölzusammensetzung nach einem der vorhergehenden Ansprüche, die ferner in einer geringeren Menge ein oder mehrere Co-Additive umfasst, die sich von Additivbestandteil (B) unterscheiden und die ausgewählt sind aus aschefreien Dispergiermitteln, Metalldetergenzien, Korrosionsinhibitoren, Antioxidantien, Stockpunktsenkungsmitteln, Antiverschleißmitteln, Reibungsmodifizierungsmitteln, Demulgatoren, Antischaummitteln und Viskositätsmodifizierungsmitteln.
  7. Verwendung eines Metalldetergenzsystems wie in einem der Ansprüche 1 bis 4 definiert in einer geringeren Menge als Additivbestandteil in einer Schmierölzusammensetzung bei der Schmierung eines kompressionsgezündeten Verbrennungsmotors, der mit Biodiesel betrieben wird, um die Korrosion der metallischen Motorkomponenten während des Betriebs des Motors zu vermindern und/oder zu inhibieren, wobei die Schmierölzusammensetzung während des Betriebs des Motors mit Biodiesel oder einem Zersetzungsprodukt desselben kontaminiert wird.
  8. Verwendung wie in Anspruch 7 beansprucht, wobei die metallischen Motorkomponenten Blei, Kupfer oder Mischungen davon umfassen.
  9. Verwendung wie in Anspruch 8 beansprucht, wobei die metallischen Motorkomponenten Blei umfassen.
  10. Verwendung wie in einem der Ansprüche 7 bis 9 beansprucht, wobei die Schmierölzusammensetzung mit mindestens 0,3 Masse-% Biodiesel oder eines Zersetzungsprodukts desselben kontaminiert ist, bezogen auf die Gesamtmasse der Schmierölzusammensetzung.
  11. Verwendung wie in einem der Ansprüche 7 bis 10 beansprucht, wobei die Schmierölzusammensetzung in einer größeren Menge Öl mit Schmierviskosität umfasst, das Basismaterial aus Gruppe III umfasst.
  12. Verfahren zum Schmieren eines kompressionsgezündeten Verbrennungsmotors, der mit Biodiesel betrieben wird, wobei der Motor mit einer Schmierölzusammensetzung wie in einem der Ansprüche 1 bis 6 beansprucht betrieben wird.
  13. Verwendung einer Schmierölzusammensetzung wie in einem der Ansprüche 1 bis 6 beansprucht, bei der Schmierung eines kompressionsgezündeten Verbrennungsmotors, der mit Biodiesel betrieben wird, zur Verminderung und/oder Inhibierung der Korrosion der metallischen Motorenkomponenten während des Betriebs des Motors.
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GB0917983A GB0917983D0 (en) 2009-10-14 2009-10-14 A lubricating oil composition
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406795A (zh) * 2015-03-24 2017-11-28 出光兴产株式会社 火花点火式内燃机用润滑油组合物、该润滑油组合物的制造方法、使用该润滑油组合物的火花点火式内燃机、以及该内燃机的润滑方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7838474B2 (en) * 2007-10-31 2010-11-23 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and a detergent
US9540586B2 (en) 2009-06-26 2017-01-10 The Lubrizol Corporation Engine oil formulations for biodiesel fuels
GB201501991D0 (en) 2015-02-06 2015-03-25 Castrol Ltd Uses and compositions
EP3585871A1 (de) 2017-02-21 2020-01-01 Exxonmobil Research And Engineering Company Schmierölzusammensetzungen und verfahren zur verwendung davon

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
NL255193A (de) 1959-08-24
NL124842C (de) 1959-08-24
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3154560A (en) 1961-12-04 1964-10-27 Monsanto Co Nu, nu'-azaalkylene-bis
US3216936A (en) 1964-03-02 1965-11-09 Lubrizol Corp Process of preparing lubricant additives
IL89210A (en) 1988-02-26 1992-06-21 Exxon Chemical Patents Inc Lubricating oil compositions containing demulsifiers
US5739088A (en) * 1990-03-14 1998-04-14 Nippon Oil Co., Ltd. Method of lubricating an alcohol-based fuel engine with an engine oil composition
GB9611318D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611428D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611424D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611316D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
US7956022B2 (en) 2005-07-29 2011-06-07 Chevron Oronite Company Llc Low sulfur metal detergent-dispersants
WO2008016484A2 (en) * 2006-07-28 2008-02-07 Exxonmobil Research And Engineering Company Lubricant compositions having improved low temperature properties
US20080182768A1 (en) * 2007-01-31 2008-07-31 Devlin Cathy C Lubricant composition for bio-diesel fuel engine applications
WO2008117776A1 (ja) * 2007-03-28 2008-10-02 Idemitsu Kosan Co., Ltd. 潤滑油組成物
JP5806802B2 (ja) * 2007-03-30 2015-11-10 出光興産株式会社 潤滑油組成物
EP2204438A4 (de) * 2007-10-16 2014-09-10 Idemitsu Kosan Co Schmierölzusammensetzung
JP5198031B2 (ja) * 2007-10-22 2013-05-15 出光興産株式会社 潤滑油組成物
US7838474B2 (en) * 2007-10-31 2010-11-23 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and a detergent
CN101960002B (zh) * 2007-12-27 2014-09-17 卢布里佐尔公司 用于生物柴油燃料的发动机油配方

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406795A (zh) * 2015-03-24 2017-11-28 出光兴产株式会社 火花点火式内燃机用润滑油组合物、该润滑油组合物的制造方法、使用该润滑油组合物的火花点火式内燃机、以及该内燃机的润滑方法

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