EP2913384B1 - A lubricating oil composition - Google Patents

A lubricating oil composition Download PDF

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Publication number
EP2913384B1
EP2913384B1 EP15151829.7A EP15151829A EP2913384B1 EP 2913384 B1 EP2913384 B1 EP 2913384B1 EP 15151829 A EP15151829 A EP 15151829A EP 2913384 B1 EP2913384 B1 EP 2913384B1
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EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
mass
equal
lubricating
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EP15151829.7A
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German (de)
English (en)
French (fr)
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EP2913384A1 (en
Inventor
Robert Shaw
Jonathan Ayutsede
Catherine Helen Frampton
Laura Ann Parsons
Stephen John Marsh
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/10—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
    • C10M2215/02—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
    • C10M2219/046—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
    • 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
    • C10N2010/04—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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/72—Extended drain
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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

Definitions

  • the present invention relates to automotive lubricating oil compositions having low levels of sulphated ash which are suitable for extended drain interval applications. More specifically, the present invention relates to such automotive lubricating oil compositions for use in gasoline (spark-ignited) and diesel (compression-ignited) internal combustion engines, especially diesel engines, crankcase lubrication, such compositions being referred to as crankcase lubricants; and to the use of additives in such compositions for extending the drain interval of the lubricating oil composition.
  • the present invention relates to automotive lubricating oil compositions, especially automotive lubricating oil compositions for use in heavy duty diesel (HDD) engines, having low levels of sulphated ash, and preferably low levels of phosphorus and also low levels of sulfur, which, in use, exhibit an extended time to reach the TBN/TAN cross-over point for the lubricant, thereby extending the drain interval of the lubricant.
  • HDD heavy duty diesel
  • 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. It is well known to include additives in crankcase lubricants for several purposes.
  • a crankcase lubricant when new has a relatively high total base number (TBN) and a relatively low total acid number (TAN).
  • TBN total base number
  • TAN total acid number
  • the TBN of a lubricant represents a measure of the quantity of basic components in the lubricant and provides an indication of the capacity of the lubricant to neutralize the acidic species produced in the lubricant and the acidic products of combustion which contaminate the lubricant, during use.
  • the TAN of a lubricant represents a measure of the quantity of acidic species present in the lubricant.
  • the TBN of a lubricant is the quantity of acid, expressed in terms of the equivalent number of milligrams of potassium hydroxide, that is required to neutralize the basic components present in 1 gram of the lubricant and it is expressed as mg KOH per gram of lubricant (mg/g KOH).
  • a lubricant having a relatively high TBN has a greater capacity to neutralize the acidic species produced in the lubricant and the acidic products of combustion which contaminate the lubricant, during use, than a lubricant having a lower TBN.
  • metal-containing or ash-forming detergents which are present in a lubricant contribute the majority of the TBN to the lubricant; the metal-containing detergents function as both detergents to reduce and remove deposits and as acid neutralizers, thereby reducing wear and corrosion and extending engine life.
  • the TAN of a lubricant is the number of milligrams of potassium hydroxide that are required to neutralize the acidic species present in 1 gram of the lubricant and it is expressed as mg KOH per gram of lubricant (mg/g KOH).
  • a lubricant having a relatively high TAN is indicative of the presence of more acidic species than a lubricant having a lower TAN.
  • the TBN of a lubricant When new, the TBN of a lubricant is relatively high and its TAN is relatively low.
  • acidic species are produced in the lubricant and the lubricant becomes contaminated with acidic species of combustion. Such acidic species are neutralized by the basic components (e.g. the metal-containing detergent) in the lubricant, thereby depleting the TBN of the lubricant.
  • the time taken, in use, to reach a point where the TBN and the TAN of the lubricant are equivalent represents one measure for determining the useful oil change interval for the lubricant, as the lubricant no longer has the ability to neutralize acidic species produced in or which may contaminate the lubricant.
  • TBN / TAN cross-over point represents one measure for determining the useful oil change interval for the lubricant, as the lubricant no longer has the ability to neutralize acidic species produced in or which may contaminate the lubricant.
  • studies have shown that when TAN exceeds TBN, engine wear and/or corrosion may accelerate at abnormally high rates. Accordingly, in order to extend the drain interval of a lubricant it is desirable to extend, in use, the time taken to reach the TBN/TAN cross-over point.
  • a lubricating oil composition which meets the ash constraints of the ACEA E6 and API CJ-4 specifications (i.e. a sulphated ash level of less than or equal to 1.0 mass % as determined by ASTM D874) and, in use, extends the time taken to reach the TBN/TAN cross-over point for the lubricant, thereby extending the drain interval of the lubricant.
  • the present invention provides a lubricating oil composition having a sulphated ash content of less than or equal to 1.0 mass % as determined by ASTM D874, the composition comprising or made by admixing:
  • the lubricating oil composition according to the present invention is a crankcase lubricant. Even more preferably, the lubricating composition according to the present invention is suitable for use in a heavy duty diesel engine.
  • the present invention provides a method of lubricating a spark-ignited or compression-ignited internal combustion engine comprising lubricating the engine with a lubricating oil composition as defined in accordance with the first aspect of the present invention.
  • the present invention provides a method of extending the time taken to reach the TBN/TAN cross-over point (i.e. extending the drain interval) of a lubricating oil composition comprising an oil of lubricating viscosity in a major amount, the method comprising admixing with the lubricating oil composition one or more oil-soluble or oil-dispersible overbased magnesium salicylate detergent(s) (B) as defined in accordance with the first aspect of the present invention, as an additive in an effective minor amount, and an oil-soluble or oil-dispersible ashless alkylene bis(dihydrocarbyldithiocarbamate) (C) as defined in accordance with the first aspect of the present invention, as an additive in an effective minor amount, and lubricating a spark-ignited or compression ignited internal combustion engine with the lubricating oil composition.
  • B oil-soluble or oil-dispersible overbased magnesium salicylate detergent(s)
  • C oil-soluble or oil-dispersible ashless alky
  • the present invention provides the use, in the lubrication of a spark-ignited or compression ignited internal combustion engine, of one or more oil-soluble or oil-dispersible overbased magnesium salicylate detergent(s) (B) as defined in accordance with the first aspect of the present invention, as an additive in an effective minor amount of greater than or equal to 0.1 mass % based on the total mass of the lubricating oil composition, in combination with an oil-soluble or oil-dispersible ashless alkylene bis(dihydrocarbyldithiocarbamate) (C) as defined in accordance with the first aspect of the present invention, as an additive in an effective minor amount of greater than or equal to 0.1 mass % based on the total mass of the lubricating oil composition, in a lubricating oil composition comprising an oil of lubricating viscosity in a major amount in excess of 50 mass % of the lubricating oil composition, to extend the drain interval of the lubricating oil composition during operation
  • the present invention provides the use, in the lubrication of a spark-ignited or compression ignited internal combustion engine, of one or more oil-soluble or oil-dispersible overbased magnesium salicylate detergent(s) (B) as defined in accordance with the first aspect of the present invention, as an additive in an effective minor amount of greater than or equal to 0.1 mass % based on the total mass of the lubricating oil composition, in combination with an oil-soluble or oil-dispersible ashless alkylene bis(dihydrocarbyldithiocarbamate) (C) as defined in accordance with the first aspect of the present invention, as an additive in an effective minor amount of greater than or equal to 0.1 mass % based on the total mass of the lubricating oil composition, in a lubricating oil composition comprising an oil of lubricating viscosity in a major amount in excess of 50 mass % of the lubricating oil composition, to extend the time taken to reach the TBN/TAN cross-over
  • the time taken to reach the TBN/TAN cross-over point of a lubricating oil composition as defined in the third and fifth aspects of the present invention and the drain interval of a lubricating oil composition as defined in the fourth aspect of the present invention is measured by employing the extended Mack T-12 engine test procedure (ASTM D7422) and running the test until the TBN/TAN cross-over point is at least reached, as described herein, and represents the time elapsed to reach the earliest specific 25 hour sampling point at which the TBN is equivalent to TAN or, if the TBN/TAN cross-over point is not met exactly at a specific 25 hour sampling point, the time elapsed to reach the first 25 hour sampling point where the TBN has fallen below TAN.
  • ASTM D7422 extended Mack T-12 engine test procedure
  • the time taken to reach the TBN/TAN cross-over point of a lubricating oil composition as defined in the third and fifth aspects of the present invention is greater than 400, more preferably greater than or equal to 425, most preferably greater than or equal to 450 hours as determined by employing the Mack T-12 engine test procedure (ASTM D7422) and running the test until the TBN/TAN cross-over point is reached, as described herein.
  • the drain interval of a lubricating oil composition as defined in the fourth aspect of the present invention is greater than 400, more preferably greater than or equal to 425, most preferably greater than or equal to 450 hours as determined by employing the Mack T-12 engine test procedure (ASTM D7422) and running the test until the TBN/TAN cross-over point is reached, as described herein.
  • the engine as defined in the second, third, fourth and fifth aspects of the present invention is a compression-ignited internal combustion engine (i.e. a diesel engine), more preferably a heavy duty diesel engine.
  • a compression-ignited internal combustion engine i.e. a diesel engine
  • a heavy duty diesel engine i.e. a diesel engine
  • the one or more overbased salicylate detergent(s) in the lubricating oil composition of the first aspect of the present invention and as defined in the second, third, fourth and fifth aspects of the present invention are the sole metal containing detergent(s) which are present in the lubricating oil composition (i.e. the only metal containing detergents which are present in the lubricating oil composition are the one or more overbased metal salicylate detergents). More preferably, the only metal containing detergents which are present in the lubricating oil composition are the one or more overbased magnesium salicylate detergents.
  • the lubricating oil composition of the first aspect of the present invention and as defined in the second, third, fourth and fifth aspects of the present invention further includes an anti-oxidant, as an additive in an effective minor amount.
  • the anti-oxidant comprises an aminic antioxidant, preferably an aromatic amine anti-oxidant, a phenolic anti-oxidant or a combination thereof, especially an aromatic amine anti-oxidant.
  • the lubricating oil composition includes both an aromatic amine and phenolic anti-oxidant.
  • the anti-oxidant(s) are ashless anti-oxidant(s).
  • the lubricating oil composition of the first aspect of the present invention and as defined in the second, third, fourth and fifth aspects of the present invention further includes an oil-soluble or oil-dispersible organo-molybdenum compound, as an additive in an effective minor amount.
  • the organo-molybdenum compound provides the lubricating oil composition with at least 10 ppm of molybdenum (ASTM D5185), based on the total mass of the lubricating oil composition.
  • the lubricating oil composition of the first aspect of the present invention and as defined in the second, third, fourth and fifth aspects of the present invention further includes a dihydrocarbyl dithiophosphate metal salt, as an additive component in an effective minor amount.
  • the lubricating oil composition of the first aspect of the present invention and as defined in the second, third, fourth and fifth aspects of the present invention further includes one or more co-additives in an effective minor amount (e.g. 5 to 25, preferably 5 to 18, more preferably 7 to 15, mass % of the one or more co-additives), other than additive components (B) and (C), selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, antifoam agents and viscosity modifiers.
  • one or more co-additives in an effective minor amount e.g. 5 to 25, preferably 5 to 18, more preferably 7 to 15, mass % of the one or more co-additives
  • additive components (B) and (C) selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, antifoam agents and viscosity modifiers
  • the lubricating oil composition of the present invention has a sulphated ash content of less than or equal to 0.95 mass % as determined by ASTM D874.
  • the lubricating oil composition of the present invention contains low levels of phosphorus.
  • the lubricating oil composition contains phosphorus in an amount of less than or equal to 0.12 mass %, preferably up to 0.11 mass %, more preferably less than or equal to 0.10 mass %, even more preferably less than or equal to 0.09 mass %, even more preferably less than or equal to 0.08 mass %, most preferably less than or equal to 0.06, mass % of phosphorus (ASTM D5185) based on the total mass of the composition.
  • the lubricating oil composition contains phosphorus in an amount of greater than or equal to 0.02, preferably greater than or equal to 0.03, mass % of phosphorus (ASTM D5185) based on the total mass of the composition.
  • the lubricating oil composition may contain low levels of sulfur.
  • the lubricating oil composition contains sulphur in an amount of up to 0.4, more preferably up to 0.3, mass % sulphur (ASTM D2622) based on the total mass of the composition.
  • the lubricating oil composition may have a total base number (TBN), as measured in accordance with ASTM D2896, of 4 to 15, preferably 5 to 15.
  • TBN total base number
  • 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 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 II or 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 II or 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 II or Group III base stock.
  • the oil of lubricating viscosity consists solely of Group II or Group III base stock. In the latter case it is acknowledged that additives included in the lubricating oil composition may comprise a carrier oil which is not a Group II or Group III base stock.
  • 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. 1.
  • 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 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 components (B) and (C), 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.
  • 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 is a multigrade oil 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 15 WX, SAE 10WX, SAE 5WX or SAE 0WX, wherein X represents any one of 20, 30, 40 and 50.
  • X is 20, 30 or 40.
  • the lubricating oil composition of the present invention requires the presence of at least one overbased magnesium salicylate detergent having a TBN of greater than or equal to 220 mg/g KOH, as measured in accordance with ASTM D2896.
  • a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it normally has acid-neutralising properties and is capable of keeping finely-divided solids in suspension.
  • Most detergents are based on metal "soaps", that is metal salts of acidic organic compounds. Accordingly, the lubricating oil composition includes a magnesium salt of salicylic acid as the metal soap.
  • Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound.
  • 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 150 or greater, and typically of from 200 to 500 or more.
  • the overbased magnesium salicylate detergent is preferably a C 8 to C 30 alkyl salicylate and mixtures thereof, with C 10 to C 20 alkyl salicylates, particularly C 14 to C 18 alkyl salicylates and mixtures thereof being particularly preferred.
  • the alkyl group(s) may be linear or branched and examples of suitable alkyl groups include: octyl; nonyl; decyl; dodecyl; pentadecyl; octadecyl; eicosyl; docosyl; tricosyl; hexacosyl; and, triacontyl.
  • the overbased magnesium salicylate detergent, as defined herein, may also include sulfurized derivatives thereof.
  • the overbased magnesium salicylate may be prepared by methods well known to those skilled in the art, for example, by reacting the appropriate salicylic acid(s) with an excess of magnesium oxide or hydroxide and an acidic gas such as carbon dioxide.
  • the salicylic acid(s) are typically prepared by carboxylation, for example by the Kolbe-Schmitt process, of phenoxides. Processes for sulfurizing the salicylic acid(s) are known to those skilled in the art.
  • the overbased magnesium salicylate detergent has a TBN of at least 250, more preferably at least 300, most preferably at least 320, mg/g KOH as determined by ASTM D2896.
  • the overbased magnesium salicylate detergent has a TBN of less than 500, most preferably less than 450, mg/g KOH as determined by ASTM D2896.
  • the overbased magnesium salicylate detergent provides the lubricating oil composition with greater than or equal to 0.05, more preferably greater than or equal to 0.06, more preferably greater than or equal to 0.07, most preferably greater than or equal to 0.10 mass % of magnesium as measured by ASTM D5185, based on the total mass of the lubricating oil composition.
  • the overbased magnesium salicylate detergent provides the lubricating oil composition with less than or equal to 0.50, even more preferably less than or equal to 0.40, most preferably less than or equal to 0.30, mass % of magnesium as measured by ASTM D5185, based on the total mass of the lubricating oil composition.
  • the overbased magnesium salicylate detergent is included in the lubricating oil composition in an amount such that total amount of sulfated ash contributed by the detergent component to the lubricant, and any other metal containing component which may be present (e.g. ZDDP), is less than or equal to 1.0, preferably less than or equal to 0.95, mass % as determined by ASTM D874.
  • the overbased magnesium salicylate detergent is included in the lubricating oil composition in an amount such that total amount of sulfated ash contributed by the detergent component to the lubricant, and any other metal containing component which may be present, is greater than or equal to 0.30, preferably greater than or equal to 0.40, mass % as determined by ASTM D874.
  • the amount of overbased magnesium detergent provides the lubricating oil composition with greater than or equal to 5, preferably greater than or equal to 7, mmoles of magnesium salicylate soap per kilogram of the lubricating oil composition.
  • the amount of overbased magnesium detergent provides the lubricating oil composition with less than or equal to 20, preferably less than or equal to 15, mmoles of magnesium salicylate soap per kilogram of the lubricating oil composition.
  • magnesium salicylate soap we mean the amount of magnesium salicylate contributed by the overbased magnesium salicylate detergent exclusive of any overbasing material.
  • the overbased magnesium salicylate detergent is present in an amount of greater than or equal to 0.1, more preferably greater than or equal to 0.2, most preferably greater than or equal to 0.5, mass % based on the total mass of the lubricating oil composition.
  • the overbased magnesium salicylate detergent is present in an amount of less than or equal to 15, more preferably less than or equal to 9, most preferably less than or equal to 5, mass % based on the total mass of the lubricating oil composition.
  • metal containing detergents may be present in the lubricating oil composition and include oil-soluble salts of neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates and naphthenates of a metal, particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, calcium and magnesium.
  • 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.
  • Detergents may be used in various combinations.
  • the one or more overbased magnesium salicylate detergent(s) represent the sole metal containing detergents in the lubricating oil composition.
  • the lubricating oil composition of the present invention requires the presence of an ashless alkylene bis(dihydrocarbyldithiocarbamate).
  • the ashless alkylene bis(dihydrocarbyldithiocarbamate) is a compound of formula (I): wherein:
  • R 1 , R 2 , R 3 and R 4 each independently represent, at each occurrence when used herein, a C 1 to C 20 hydrocarbyl group. More preferably, R 1 , R 2 , R 3 and R 4 each independently represent, at each occurrence when used herein, a branched or linear (i.e. unbranched) C 1 to C 16 alkyl group or a substituted or unsubstituted aryl group. Even more preferably, R 1 , R 2 , R 3 and R 4 each independently represent, at each occurrence when used herein, a branched or linear C 1 to C 16 alkyl group, a C 1 to C 16 alkyl substituted aryl group or an unsubstituted aryl group.
  • R 1 , R 2 , R 3 and R 4 each independently represent, at each occurrence when used herein, a branched or linear C 1 to C 16 alkyl group, a C 1 to C 16 alkyl substituted phenyl group or an unsubstituted phenyl group.
  • R 1 , R 2 , R 3 and R 4 each independently represent a substituted or unsubstituted aryl group as defined herein, then the appropriate nitrogen atom of a compound of formula I is bonded to a carbon atom of the aryl ring of the appropriate substituted or unsubstituted aryl group by a nitrogen to carbon single bond.
  • R 1 , R 2 , R 3 and R 4 each independently represent a branched or linear C 1 to C 16 alkyl group, especially a branched or linear C 1 to C 10 alkyl group.
  • R 1 , R 2 , R 3 and R 4 are identical.
  • R 1 , R 2 , R 3 and R 4 each independently represent a C 1 to C 16 alkyl substituted aryl group or an unsubstituted aryl group, more preferably a C 1 to C 16 alkyl substituted phenyl group or an unsubstituted phenyl group, even more preferably a C 3 to C 16 alkyl substituted phenyl group.
  • R 1 , R 2 , R 3 and R 4 are identical.
  • R 1 and R 3 are identical, and R 2 and R 4 are identical.
  • X in a compound of formula I represents a C 1 to C 10 alkylene group. More preferably, X in a compound of formula I represents (CH 2 )n where n is an integer from 1 to 20, preferably an integer from 1 to 10, more preferably an integer from 1 to 5, especially 1 (i.e. X represents methylene when n is 1).
  • Highly preferred compounds of formula I include: methylene bis(N-n-octyl-N-phenyldithiocarbamate); methylene bis(di(nonylphenyl)dithiocarbamate) - wherein each nitrogen atom of the dithiocarbamate is bonded to two phenyl rings, each of said rings are substituted with a C 9 alkyl group; and, methylene bis(dibutyldithiocarbamate).
  • An especially preferred compound of formula I is methylene bis(dibutyldithiocarbamate).
  • the ashless alkylene bis(dihyrocarbyldithiocarbamates) may be prepared by methods well known to those skilled in the art. For example, an appropriate amine may be reacted with sodium hydride, the resulting product reacted with carbon disulphide, and the resulting product reacted with a dihaloalkane, e.g. iodomethane.
  • a dihaloalkane e.g. iodomethane.
  • methylene bis(N-n-octyl-N-phenyldithiocarbamate) and methylene bis(di(nonylphenyl)dithiocarbamate) may be prepared as described in European patent application EP 2,692,840A and methylene bis(dibutyldithiocarbamate) is commercially available and sold under the trade name of Vanlube 7723 by Vanderbilt Chemicals LLC, USA.
  • the ashless alkylene bis(dihydrocarbyldithiocarbamate) is present in an amount of greater than or equal to 0.1, more preferably greater than or equal to 0.2, mass %, based on the total mass of the lubricating oil composition.
  • the ashless alkylene bis(dihydrocarbyldithiocarbamate) is present in an amount of less than or equal to 5.0, more preferably less than or equal to 3.0, even more preferably less than or equal to 2.0, most preferably less than or equal to 1.0, mass %, based on the total 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 internal combustion engines, particularly 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 engine comprises a compression-ignited internal combustion engine, especially a heavy duty diesel engine.
  • the lubricating oil compositions are crankcase lubricants.
  • 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.
  • the lubricating oil composition includes one or more co-additives in a minor amount, other than additive components (B) and (C), selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, antifoam agents and viscosity modifiers.
  • additive components (B) and (C) selected from ashless dispersants, metal detergents, corrosion inhibitors, antioxidants, pour point depressants, antiwear agents, friction modifiers, demulsifiers, antifoam agents and viscosity modifiers.
  • 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", 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 ; US-A-3,154,560 ; US-A-3,172,892 ; US-A-3,024,195 ; US-A-3,024,237 , US-A-3,219,666 ; and US-A-3,216,936 , that may be post-treated to improve their properties, such as borated (as described in US-A-3,087,936 and US-A-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.
  • 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 or oil-dispersible organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition. Suitable oil-soluble or oil-dispersible organo-molybdenum compounds have a molybdenum-sulfur core.
  • 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 oil-soluble or oil-dispersible 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 oil-soluble or oil-dispersible organo-molybdenum compounds may be present in the lubricating oil composition in an amount of greater than or equal to 0.02, preferably greater than or equal to 0.05, mass % based on the total mass of the lubricating oil composition.
  • the oil-soluble or oil-dispersible organo-molybdenum compounds may be present in the lubricating oil composition in an amount of less than or equal to 2.0, preferably less than or equal to 1.0, even more preferably less than or equal to 0.5, mass % based on the total mass of the lubricating oil composition.
  • the oil-soluble or oil-dispersible organo-molybdenum compound provides the lubricant with greater than or equal to 10, preferably greater than or equal to 20, more preferably greater than or equal to 30, ppm of molybdenum (ASTM D5185) based on the total mass of the lubricating oil composition.
  • oil-soluble or oil-dispersible organo-molybdenum compound provides the lubricant with less than or equal to 1500, preferably less than or equal to 1000, more preferably less than or equal to 700, ppm of molybdenum (ASTM D5185) based on the total mass of the lubricating oil composition.
  • 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, aromatic amines, particularly secondary aromatic amines having at least two aromatic (e.g. phenyl groups) groups attached directly to the nitrogen atom, 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).
  • the lubricating oil composition in all aspects of the present invention includes an anti-oxidant, more preferably an ashless anti-oxidant.
  • the anti-oxidant when present, is an aromatic amine anti-oxidant, a phenolic anti-oxidant or a combination thereof, especially an aromatic amine anti-oxidant.
  • the lubricating oil composition in all aspects of the present invention includes both an aromatic amine and phenolic anti-oxidant. Accordingly, the aromatic amine and/or phenolic anti-oxidants, when present, are ashless anti-oxidants.
  • the total amount of anti-oxidant (e.g. aromatic amine anti-oxidant, a phenolic anti-oxidant or a combination thereof) which may be present in the lubricating oil composition is greater than or equal to 0.05, preferably greater than or equal to 0.1, even more preferably greater than or equal to 0.2, mass % based on the total mass of the lubricating oil composition.
  • the total amount of anti-oxidant which may be present in the lubricating oil composition is less than or equal to 5.0, preferably less than or equal to 3.0, even more preferably less than or equal to 2.5, mass % based on the total mass of 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.
  • 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 (ZDDPs) 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).
  • ZDDPs 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 0.12, more preferably 0.02 to 0.11, even more preferably 0.02 to 0.10, even more preferably 0.02 to 0.09, even more preferably 0.02 to 0.08 mass %, most preferably 0.02 to 0.06, mass % of phosphorus as measured in accordance with ASTM D5185, based on the total mass of the composition.
  • the dihydrocarbyl dithiophosphate metal salt should preferably be added to the lubricating oil compositions in amounts no greater than 1.5 mass % (a.i.), based upon the total mass of the lubricating oil composition.
  • ashless anti-wear agents examples include 1,2,3-triazoles, benzotriazoles and sulfurised fatty acid esters.
  • 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 fumarate/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 TBN/TAN cross-over point of a lubricant is evaluated using an extended Mack T-12 engine test procedure as described in ASTM D7422; this test method is commonly referred to as the Mack T-12.
  • the Mack T-12 engine test procedure is a standard engine-dynamometer test for evaluating the ability of a diesel engine lubricant to control lead corrosion, oil consumption, and wear of piston rings and cylinder liners in an engine equipped with Exhaust Gas Recirculation (EGR) and running on ultra-low sulphur diesel (ULSD).
  • EGR Exhaust Gas Recirculation
  • ULSD ultra-low sulphur diesel
  • the Mack T-12 test employs a Mack E-TECH V-MAC III diesel engine equipped with exhaust gas recirculation (EGR).
  • the diesel engine is an in-line, six cylinder, four-stroke, turbocharged engine with 12 litre displacement.
  • the standard Mack T-12 procedure is a two phase test lasting 300-hours where the engine in each phase is run at constant speed and load. The first 100-hour phase has retarded injection timing to produce soot in the oil.
  • the second 200-hour phase is run at heavy load to promote piston ring and cylinder liner wear.
  • the steady-state operating parameters for the two phases are set out in Table 1 of ASTM D7422.
  • the Mack T-12 test the engine initially includes 32.7 kg of lubricant and after the 100 hour point, i.e. after completion of Phase 1, 2.27 kg of fresh lubricant is added at every 50-hour interval. If necessary, used lubricant is removed first so that the lubricant mass is below the full mark by 2.27kg.
  • the test procedure is run for an extended time.
  • the engine is continued to run under the Phase 2 conditions until the TBN/TAN cross-over point is at least reached, more preferably for 50-hours afterwards, up to a maximum test length of 600-hours.
  • the initial TBN and TAN of a lubricant are measured in accordance with ASTM D4739 and D664, respectively, prior to the Mack T-12 test.
  • a sample of the lubricant 120 ml is removed from the engine at 25-hours intervals throughout the test for physical and chemical analysis.
  • the TBN (ASTM D4739) and the TAN (ASTM D664) of the lubricant sample is measured and recorded.
  • the TBN/TAN cross-over point represents the earliest specific 25 hour sampling point at which the TBN is equivalent to TAN or, if the TBN/TAN cross-over point is not met exactly at a specific 25 hour sampling point, the first 25 hour sampling point where the TBN has fallen below TAN.
  • a series of 15W/40 multigrade lubricating oil compositions of essentially equal sulfated ash (ASTM D874) were prepared by admixing a Group II base stock with known additives, as detailed herein.
  • Each of the Comparative lubricating oil compositions and the Inventive lubricating oil compositions included identical amounts of the following additives which are available from Infineum UK Ltd: a dispersant (4.75 mass %); a tri-nuclear organo molybdenum compound; an anti-foam; a pour point depressant; and, a viscosity modifier. Further details of the composition of each lubricant is set out below, where Lubricants A to C are comparative lubricants and lubricants 1 and 2 represent lubricants of the present invention:
  • Lubricants A to C and Lubricants 1 and 2 with the exception of methylene bis(dibutylditiocarbamate), are available from Infineum UK Ltd; methylene bis(dibutylditiocarbamate) is sold under the trade name of Vanlube 7723 and is available from Vanderbilt Chemicals LLC, USA.

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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)
EP15151829.7A 2014-02-26 2015-01-20 A lubricating oil composition Active EP2913384B1 (en)

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EP3263676B1 (en) * 2016-06-30 2023-07-19 Infineum International Limited Lubricating oil compositions
FR3092337B1 (fr) * 2019-02-04 2021-04-23 Total Marketing Services Composition lubrifiante pour prévenir le pré-allumage
WO2020190859A1 (en) 2019-03-20 2020-09-24 Basf Se Lubricant composition

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SG10201500563WA (en) 2015-09-29
GB2525479A (en) 2015-10-28
GB2525479B (en) 2016-08-03
CN104862030A (zh) 2015-08-26
CN104862030B (zh) 2019-08-20
GB201503263D0 (en) 2015-04-15
BR102015004102A2 (pt) 2016-03-08
BR102015004102B1 (pt) 2021-11-09
JP2015160956A (ja) 2015-09-07
US20150240181A1 (en) 2015-08-27
CA2883416C (en) 2022-04-19
JP6559974B2 (ja) 2019-08-14
CA2883416A1 (en) 2015-08-26

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