EP2363454B1 - Verwendung einer schmierölzusammensetzung - Google Patents

Verwendung einer schmierölzusammensetzung Download PDF

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Publication number
EP2363454B1
EP2363454B1 EP10196988.9A EP10196988A EP2363454B1 EP 2363454 B1 EP2363454 B1 EP 2363454B1 EP 10196988 A EP10196988 A EP 10196988A EP 2363454 B1 EP2363454 B1 EP 2363454B1
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EP
European Patent Office
Prior art keywords
mass
lubricating oil
copolymer
isoprene
oil composition
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.)
Revoked
Application number
EP10196988.9A
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English (en)
French (fr)
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EP2363454A1 (de
Inventor
Stuart James Mctavish
Keith Strickland
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Infineum International Ltd
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Infineum International Ltd
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Priority to EP10196988.9A priority Critical patent/EP2363454B1/de
Publication of EP2363454A1 publication Critical patent/EP2363454A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/073—Star shaped polymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—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
    • C10N2030/78—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
    • C10N2040/252—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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02—Reduction, e.g. hydrogenation

Definitions

  • the present invention relates to automotive lubricating oil compositions, more especially to automotive lubricating oil compositions for use in gasoline (spark-ignited) and diesel (compression-ignited) internal combustion engines fuelled at least in part with a biofuel, especially compression-ignited internal combustion engines fuelled at least in part with a biodiesel fuel and spark-ignited internal combustion engines fuelled at least in part with bioethanol 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, which exhibit improved anti-oxidant properties during operation of the engine which is fuelled with a biofuel; and to the use of additives in such compositions for improving the anti-oxidant 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 oxidation of the lubricant.
  • 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 oxidation of the lubricant 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 oxidation of the lubricant 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.
  • a similar increase in the oxidation of the lubricant has also been found to occur in spark-ignited internal combustion engines fuelled at least in part with an alcohol based fuel (e.g. bioethanol) due to the presence of the alcohol based fuel and the decomposition products thereof in the crankcase lubricant. Oxidation of the lubricant typically yields corrosive acids and an undesirable increase in viscosity, thereby shortening the useful life of the lubricant. Accordingly, lubricants with improved antioxidant properties need to be identified.
  • an alcohol based fuel e.g. bioethanol
  • EP2055762 discloses the use of diarylamine oxidation inhibitors to improve the oxidation stability of lubricants contaminated with biodiesel.
  • the present invention is based on the discovery that a lubricating oil composition can be formulated which exhibits significantly improved antioxidant properties in the presence of a biofuel.
  • the present invention provides the use, in the lubrication of a compression-ignited internal combustion engine which is fuelled with biodiesel, of an oil-soluble or oil-dispersible viscosity index improver (B) which is a linear or star-shaped polymer which is derived from the polymerisation of one or more conjugated diene monomers, as an additive component in a minor amount of from 0.01 to 20 mass % based on the mass of the lubricating oil composition, in a lubricating oil composition, to reduce and/or inhibit oxidation of the lubricating oil composition during operation of the engine and wherein the lubricating oil composition becomes contaminated with biodiesel or a decomposition product thereof during operation of the engine.
  • B oil-soluble or oil-dispersible viscosity index improver
  • the lubricating oil composition is a crankcase lubricant.
  • a viscosity index improver comprising a linear or star-shaped polymer which is derived from the polymerisation of one or more conjugated diene monomers, in a lubricating oil composition, particularly one including a Group III base stock, improves the antioxidant properties of the lubricant, in use, in the lubrication of a compression-ignited internal combustion engine which is fuelled with biodiesel.
  • the inclusion of such a viscosity index improver in a lubricating oil composition comprising a Group III base stock provides, in use, a positive credit in terms of reduced oxidation of the lubricant and/or may promote the useful life of the lubricant.
  • the lubricating oil composition comprises a major amount of an oil of lubricating viscosity comprising a Group III base stock.
  • a lubricating oil composition comprising: (A) an oil of lubricating viscosity in a major amount, comprising a Group III base stock; and, (B) as an additive component in a minor amount, an oil-soluble or oil-dispersible viscosity index improver comprising a linear or star-shaped polymer which is derivable, at least in part, from the polymerisation of one or more conjugated diene monomers, to reduce and/or inhibit oxidation of the lubricating oil composition, during operation of the engine.
  • the lubricating oil compositions as defined in the first aspect of the invention is contaminated with at least 0.3 mass %, based on the total mass of the lubricating oil composition, of biodiesel or a decomposition product thereof and mixtures thereof.
  • the viscosity index improver comprises a linear or star-shaped, at least partially hydrogenated, polymer which is derived from the polymerisation of one or more conjugated diene monomers.
  • the compression-ignited internal combustion engine is fuelled at least in part with a biodiesel fuel.
  • 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: a) Group I base stocks contain less than 90 percent saturates and/or greater than 0.03 percent sulphur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1. b) Group II base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulphur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1.
  • Group III base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulphur and have a viscosity index greater than or equal to 120 using the test methods specified in Table E-1.
  • Group IV base stocks are polyalphaolefins (PAO).
  • Group V base stocks include all other base stocks not included in Group I, II, III, or IV. Table E-1: Analytical Methods for Base Stock Property Test Method Saturates ASTM D 2007 Viscosity Index ASTM D 2270 Sulphur ASTM D 2622 ASTM D 4294 ASTM D 4927 ASTM D 3120
  • 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 oil of lubricating viscosity consists solely of 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 III base stock.
  • oils of lubricating viscosity which may be included in the lubricating oil composition are detailed as follows: Natural oils include animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • 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 the oil-soluble or oil-dispersible viscosity index improver 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.
  • compositions comprise defined components that may or may not remain the same chemically before and after mixing with an oleaginous carrier.
  • Compositions are encompassed 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 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 may have a total base number (TBN) of 4 to 15, preferably 5 to 12.
  • TBN total base number
  • HDD heavy duty diesel
  • the TBN of the lubricating composition ranges from about 4 to 12, such as 6 to 12.
  • PCDO passenger car diesel engine lubricating oil composition
  • PCMO passenger car motor oil for a spark-ignited engine
  • the TBN of the lubricating composition ranges from about 5.0 to about 12.0, such as from about 5.0 to about 11.0.
  • 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.
  • Additive component B comprises a viscosity index improver (or viscosity modifier).
  • Viscosity index improvers for lubricating oil compositions advantageously increase the viscosity of the lubricating oil composition at higher temperatures when used in relatively small amounts (have a high thickening efficiency (TE)), provide reduced lubricating oil resistance to cold engine starting (as measured by "CCS" performance) and resist mechanical degradation and reduction in molecular weight in use (have a high shear stability index (SSI)). It is also preferred that the viscosity index improver displays soot-dispersing characteristics in lubricating oil compositions. These oil-soluble polymers are generally of high molecular weight (M n > 50,000) compared to the base oil and other components.
  • Crankcase lubricating oil compositions conventionally contain viscosity index improvers to improve the viscometric performance of the engine oil, i.e., to provide multigrade oils such as SAE 5W-30, 10W-30 and 10W-40.
  • Viscosity index improvers useful in the practice of the present invention comprise linear or star-shaped polymers which are derived from the polymerisation of one or more conjugated diene monomers.
  • the linear and star-shaped polymers are at least partially or fully hydrogenated.
  • Conjugated diene monomers contain two double bonds located in conjugation with each other, generally in a 1,3 relationship. Conjugated dienes containing more than two doudle bonds are also considered within the definition of "conjugated diene monomers ", provided at least two of the double bonds are located in conjugation with each other.
  • Preferred conjugated diene monomers useful in the formation of the viscosity index improvers include conjugated dienes containing from 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, for example, 1,3-butadiene, isoprene, piperylene, 4-methylpenta-1,3-diene, 2-phenyl-1,3-butadiene, 3,4-dimethyl-1,3-hexadiene and 4,5-diethyl-1,3-octadiene.
  • Highly preferred conjugated diene monomers include 1,3-butadiene, isoprene, or mixtures thereof; especially isoprene.
  • Preferred isoprene monomers that may be used as the precursors of the viscosity index improver polymers can be incorporated into the polymer as either 1,4- or 3,4-configuration units, and mixtures thereof.
  • the majority of the isoprene is incorporated into the polymer as 1,4-units, such as greater than about 60 mass %, more preferably greater than about 80 mass %, such as about 80 to 100 mass %, most preferably greater than about 90 mass %., such as about 93 mass % to 100 mass %.
  • Preferred butadiene monomers that may be used as the precursors of the viscosity index improver polymers can be incorporated into the polymer as either as either 1,2- or 1,4-configuration units.
  • At least about 70 mass % such as at least about 75 mass %, more preferably at least about 80 mass %, such as at least about 85 mass %, most preferably at least about 90, such as 95 to 100 mass %, of the butadiene is incorporated into the polymer as 1,4- units.
  • the viscosity index improver comprises a linear polymer, especially a linear diblock copolymer comprising at least one block derivable predominantly from a vinyl aromatic hydrocarbon monomer and at least one block derivable predominantly from said one or more conjugated diene monomers.
  • Useful vinyl aromatic hydrocarbon monomers include those containing from 8 to 16 carbon atoms, for example: styrene; alkyl-substituted styrene; alkoxy-substitued styrene; vinyl naphthalene and alkyl-substituted vinyl naphthalene.
  • the alkyl and alkoxy substituents include 1 to 6 carbon atoms.
  • Highly preferred vinyl aromatic hydrocarbon monomers include styrene, alkyl-substituted styrene, alkoxy-substitued styrene; especially, styrene.
  • Linear diblock copolymers useful in the practice of the present invention may be represented by the following general formula: A z -(B-A) y -B x wherein:
  • linear diblock copolymers are tapered linear block copolymers represented by the following general formula: A-A/B-B wherein:
  • prodominantly means that the specified monomer or monomer type that is the principle component in that polymer block is present in an amount of at least 85 mass % of the block.
  • Polymers prepared with diolefins will contain ethylenic unsaturation, and such polymers are preferably hydrogenated.
  • the hydrogenation may be accomplished using any of the techniques known in the prior art.
  • the hydrogenation may be accomplished such that both ethylenic and aromatic unsaturation is converted (saturated) using methods such as those taught, for example, in U.S. Pat. Nos. 3,113,986 and 3,700,633 or the hydrogenation may be accomplished selectively such that a significant portion of the ethylenic unsaturation is converted while little or no aromatic unsaturation is converted as taught, for example, in U.S. Pat. Nos.
  • the linear diblock copolymer is hydrogenated wherein at least 50%, preferably at least 70%, more preferably at least 90%, most preferably at least 95 mass % of the original olefinic unsaturation is hydrogenated.
  • the block copolymers may include mixtures of linear polymers as disclosed above, having different molecular weights and/or different vinyl aromatic contents as well as mixtures of linear diblock copolymers having different molecular weights and/or different vinyl aromatic contents.
  • the use of two or more different polymers may be preferred to a single polymer depending on the rheological properties the product is intended to impart when used to produce formulated engine oil.
  • the linear polymer may have a number average molecular weight of between 200,000 and 1,500,000. A number average molecular weight of between 350,000 and 900,000 is preferred.
  • the amount of vinyl aromatic content of the copolymer is preferably between 5% and 40% by mass of the copolymer. For such copolymers, number average molecular weights between 85,000 and 300,000 are acceptable.
  • number average molecular weight refers to the number average weight as measured by Gel Permeation Chromatography ("GPC") with a polystyrene standard, subsequent to hydrogenation.
  • Useful block copolymers include those prepared in bulk, suspension, solution or emulsion.
  • polymerization of monomers to produce hydrocarbon polymers may be accomplished using free-radical, cationic and anionic initiators or polymerization catalysts, such as transition metal catalysts used for Ziegler-Natta and metallocene type (also referred to as "single-site") catalysts.
  • the linear diblock copolymer is at least one linear diblock copolymer having a polystyrene block and a block derived from isoprene, butadiene, or a mixture thereof. More preferably, the linear diblock copolymer is at least one linear diblock copolymer selected from hydrogenated styrene/butadiene diblock copolymers and hydrogenated styrene/isoprene diblock copolymers.
  • the diblock copolymer has a Shear Stability Index value, determined in accordance with the procedure of ASTM D6278-98 (known as the Kurt-Orban (KO) or DIN bench test), of from 2 to 50%, more preferably from 5 to 50% (30 cycles), and the block of the diblock copolymer derived from diene comprises from 40 to 90 mass % derived from isoprene and from 10 to 60 mass % derived from butadiene.
  • KO Kurt-Orban
  • Diblock copolymer components used in the present invention are available as commercial products.
  • Examples of commercially available styrene/hydrogenated isoprene linear diblock copolymers include Infineum SV140TM, Infineum SV150TM, Infineum SV151TM and Infineum SV160TM, available from Infineum USA L.P. and Infineum UK Ltd.; Lubrizol® 7318, available from The Lubrizol Corporation; and Septon 1001TM and Septon 1020TM, available from Septon Company of America (Kuraray Group).
  • Suitable styrene/1,3-butadiene hydrogenated block copolymers are sold under the tradename GlissoviscalTM by BASF.
  • the viscosity index improver comprises at least one star-shaped, at least partially hydrogenated, polymer derived from the polymerisation of one or more conjugated diene monomers as defined hereinbefore.
  • the star-shaped polymer includes multiple arms extending from a central core; the arms being derived from the polymerisation of one or more conjugated diene monomers as defined hereinbefore, and optionally a vinyl aromatic hydrocarbon monomer as defined hereinbefore.
  • the arms of the star polymer may be a homopolymer derived essentially from the polymerisation of a single conjugated diene monomer as defined herein, such as isoprene or 1,3-butadiene, particularly isoprene.
  • the arms of the star polymer may be a copolymer derived essentially from the polymerisation of two or more conjugated diene monomers as defined herein, such as an isoprene and 1,3-butadiene copolymer, or a copolymer derived essentially from the polymerisation of one or more conjugated diene monomers as defined herein and a vinyl aromatic hydrocarbon monomer as defined herein, such as an isoprene-styrene copolymer, a butadiene-styrene copolymer or an isoprene-butadiene-styrene copolymer.
  • derived essentially permits the inclusion of other substances not materially affecting the characteristics of the polymer to which it applies.
  • derived essentially means the specified monomer and comonomers, in the case of a copolymer, are present in an amount of at least 90 %, more preferably 95 %, even more preferably greater than 99 % by mass of the polymer.
  • the arms of the star polymer may also be a block copolymer, preferably a linear block copolymer, more preferably a linear diblock copolymer, such as one represented by the following general formula: A z -(B-A) y -B x wherein:
  • the arms of the star polymer may also be a tapered linear block copolymer such as one represented by the following general formula: A-A/B-B wherein:
  • the arms of the star polymer comprise a hydrogenated isoprene-butadiene copolymer, a hydrogenated styrene-isoprene-butadiene copolymer, a hydrogenated isoprene-styrene copolymer or a hydrogenated butadiene-styrene copolymer.
  • the arms of the star polymer comprise a linear diblock copolymer as defined herein.
  • the linear diblock copolymer comprises at least one block derivable predominantly from a vinyl aromatic hydrocarbon monomer as defined herein and at least one block derivable predominantly from one or more conjugated diene monomers as defined herein.
  • the vinyl aromatic hydrocarbon monomer comprises styrene.
  • the one or more conjugated diene monomers comprise isoprene, butadiene or a mixture thereof.
  • the linear diblock copolymer is at least partially hydrogenated.
  • the at least one block derived predominantly from a vinyl aromatic hydrocarbon monomer (e.g. styrene) in the linear diblock copolymer is present in an amount of up to 35 %, even more preferably up to 25 %, most preferably 5 to 25 %, by mass based on the total mass of the linear diblock copolymer.
  • a vinyl aromatic hydrocarbon monomer e.g. styrene
  • the at least one block derived from predominantly from one or more conjugated diene monomers is present in an amount of greater than 65 %, even more preferably greater than or equal to 75 %, most preferably 75 to 95 %, by mass based on the total mass of the linear diblock copolymer.
  • the linear diblock copolymer comprises at least one polystyrene block and a block derived from isoprene, butadiene, or a mixture thereof.
  • Highly preferred linear diblock copolymers comprise linear diblock copolymers including at least one linear diblock copolymer selected from hydrogenated styrene/isoprene diblock copolymers, hydrogenated styrene/butadiene diblock copolymers and hydrogenated styrene/isoprene-butadiene diblock copolymers.
  • the linear diblock copolymer comprises at least one isoprene-butadiene block
  • the block is derived predominantly from 70 to 90 mass % isoprene monomers and 30 to 10 mass % 1,3-butadiene monomers.
  • the arms of the star polymer typically comprise a copolymer derived from 70 to 90 mass % isoprene monomers and 30 to 10 mass % 1,3-butadiene monomers. More preferably, the arms of the star polymer further include a vinyl aromatic hydrocarbon monomer as defined herein, particularly styrene.
  • a highly preferred copolymer is derived from isoprene monomers, 1,3-butadiene monomers and a vinyl aromatic hydrocarbon monomer, especially styrene.
  • the vinyl aromatic hydrocarbon monomer may be present in an amount of up to 35 mass %, preferably up to 25 mass %, based on the total mass of the copolymer.
  • the arms of the star polymer are formed via anionic polymerization to form a living polymer.
  • Anionic polymerization has been found to provide copolymers having a narrow molecular weight distribution (Mw/Mn), such as a molecular weight distribution of less than about 1.2
  • living polymers may be prepared by anionic solution polymerization of a mixture of the conjugated diene monomers in the presence of an alkali metal or an alkali metal hydrocarbon, e.g., sodium naphthalene, as anionic initiator.
  • an alkali metal or an alkali metal hydrocarbon e.g., sodium naphthalene
  • the preferred initiator is lithium or a mono lithium hydrocarbon.
  • Suitable lithium hydrocarbons include unsaturated compounds such as allyl lithium, methallyl lithium; aromatic compounds such as phenyl lithium, the tolyl lithiums, the xylyl lithiums and the naphthyl lithiums, and in particular, the alkyl lithiums such as methyl lithium, ethyl lithium, propyl lithium, butyl lithium, amyl lithium, hexyl lithium, 2-ethylhexyl lithium and n-hexadecyl lithium.
  • Secondary-butyl lithium is the preferred initiator.
  • the initiator(s) may be added to the polymerization mixture in two or more stages, optionally together with additional monomer.
  • the living polymers are olefinically unsaturated.
  • the solvents in which the living polymers are formed are inert liquid solvents, such as hydrocarbons e.g., aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, cyclohexane, methylcyclohexane, or aromatic hydrocarbons e.g., benzene, toluene, ethylbenzene, the xylenes, diethylbenzenes, propylbenzenes. Cyclohexane is preferred. Mixtures of hydrocarbons e.g., lubricating oils, may also be used.
  • hydrocarbons e.g., aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, cyclohexane
  • the temperature at which the polymerization is conducted may be varied within a wide range, such as from about -50°C to about 150°C, preferably from about 20°C to about 80°C.
  • the reaction is suitably carried out in an inert atmosphere, such as nitrogen, and may optionally be carried out under pressure e.g., a pressure of from about 0.5 to about 10 bars.
  • the concentration of the initiator used to prepare the living polymer may also vary within a wide range and is determined by the desired molecular weight of the living polymer.
  • the living polymers formed via the foregoing process are reacted in an additional reaction step, with a polyalkenyl coupling agent.
  • Polyalkenyl coupling agents capable of forming star polymers have been known for a number of years and are described, for example, in U.S. Patent No. 3,985,830 .
  • Polyalkenyl coupling agents are conventionally compounds having at least two non-conjugated alkenyl groups. Such groups are usually attached to the same or different electron-withdrawing moiety e.g. an aromatic nucleus.
  • Such compounds have the property that at least of the alkenyl groups are capable of independent reaction with different living polymers and in this respect are different from conventional conjugated diene polymerizable monomers such as butadiene, isoprene, etc.
  • Pure or technical grade polyalkenyl coupling agents may be used.
  • Such compounds may be aliphatic, aromatic or heterocyclic. Examples of aliphatic compounds include the polyvinyl and polyallyl acetylene, diacetylenes, phosphates and phosphates as well as dimethacrylates, e.g. ethylene dimethylacrylate. Examples of suitable heterocyclic compounds include divinyl pyridine and divinyl thiophene.
  • the preferred coupling agents are polyalkenyl aromatic compounds and most preferred are the polyvinyl aromatic compounds.
  • examples of such compounds include those aromatic compounds, e.g. benzene, toluene, xylene, anthracene, naphthalene and durene, which are substituted with at least two alkenyl groups, preferably attached directly thereto.
  • Specific examples include the polyvinyl benzenes e.g.
  • divinyl, trivinyl and tetravinyl benzenes divinyl, trivinyl and tetravinyl ortho-, meta- and para-xylenes, divinyl naphthalene, divinyl ethyl benzene, divinyl biphenyl, diisobutenyl benzene, diisopropenyl benzene, and diisopropenyl biphenyl.
  • divinyl benzene containing other monomers e.g. styrene and ethyl styrene
  • the coupling agents may be used in admixture with small amounts of added monomers which increase the size of the nucleus, e.g. styrene or alkyl styrene.
  • the nucleus can be described as a poly(dialkenyl coupling agent/monoalkenyl aromatic compound) nucleus, e.g. a poly(divinylbenzene/monoalkenyl aromatic compound) nucleus.
  • the polyalkenyl coupling agent should be added to the living polymer after the polymerization of the monomers is substantially complete, i.e. the agent should be added only after substantially all the monomer has been converted to the living polymers.
  • the amount of polyalkenyl coupling agent added may vary within a wide range, but preferably, at least 0.5 mole of the coupling agent is used per mole of unsaturated living polymer. Amounts of from about 1 to about 15 moles, preferably from about 1.5 to about 5 moles per mole of living polymer are preferred. The amount, which can be added in two or more stages, is usually an amount sufficient to convert at least about 80 mass % to 85 mass % of the living polymer into star-shaped polymer.
  • the coupling reaction can be carried out in the same solvent as the living polymerization reaction.
  • the coupling reaction can be carried out at temperatures within a broad range, such as from 0°C to 150°C, preferably from about 20°C to about 120°C.
  • the reaction may be conducted in an inert atmosphere, e.g. nitrogen, and under pressure of from about 0.5 bar to about 10 bars.
  • the star polymers thus formed are characterized by a dense centre or nucleus of crosslinked poly(polyalkenyl coupling agent) and a number of arms of substantially linear unsaturated polymers extending outwardly from the nucleus.
  • the number of arms may vary considerably, but is typically between about 4 and 25.
  • the resulting star polymers can then be hydrogenated using any suitable means.
  • a hydrogenation catalyst may be used e.g. a copper or molybdenum compound. Catalysts containing noble metals, or noble metal-containing compounds, can also be used.
  • Preferred hydrogenation catalysts contain a non-noble metal or a non-noble metal-containing compound of Group VIII of the periodic Table i.e., iron, cobalt, and particularly, nickel. Specific examples of preferred hydrogenation catalysts include Raney nickel and nickel on kieselguhr.
  • Particularly suitable hydrogenation catalysts are those obtained by causing metal hydrocarbyl compounds to react with organic compounds of any one of the group VIII metals iron, cobalt or nickel, the latter compounds containing at least one organic compound that is attached to the metal atom via an oxygen atom as described, for example, in U.K. Patent No. 1,030,306 .
  • nickel diisopropyl salicylate nickel naphthenate, nickel 2-ethyl hexanoate, nickel di-tert-butyl benzoate, nickel salts of saturated monocarboxylic acids obtained by reaction of olefins having from 4 to 20 carbon atoms in the molecule with carbon monoxide and water in the presence of acid catalysts) or with nickel enolates or phenolates (e.g., nickel acetonylacetonate, the nickel salt of butylacetophenone).
  • Suitable hydrogenation catalysts will be well known to those skilled in the art and the foregoing list is by no means intended to be exhaustive.
  • the hydrogenation of the star polymer is suitably conducted in solution, in a solvent which is inert during the hydrogenation reaction.
  • a solvent which is inert during the hydrogenation reaction.
  • Saturated hydrocarbons and mixtures of saturated hydrocarbons are suitable.
  • the hydrogenation solvent is the same as the solvent in which polymerization is conducted.
  • at least 50%, preferably at least 70%, more preferably at least 90%, most preferably at least 95% by mass of the original olefinic unsaturation is hydrogenated.
  • the hydrogenated star polymer may then be recovered in solid form from the solvent in which it is hydrogenated by any convenient means, such as by evaporating the solvent.
  • oil e.g. lubricating oil may be added to the solution, and the solvent stripped off from the mixture so formed to provide a concentrate.
  • Suitable concentrates contain from about 3 mass % to about 25 mass %, preferably from about 5 mass % to about 15 mass % of the hydrogenated star polymer VI improver.
  • the star polymers useful in the practice of the present invention can have a number average molecular weight of from about 10,000 to 700,000, preferably from about 30,000 to 500,000.
  • number average molecular weight refers to the number average weight as measured by Gel Permeation Chromatography ("GPC") with a polystyrene standard, subsequent to hydrogenation. It is important to note that, when determining the number average molecular weight of a star polymer using this method, the calculated number average molecular weight will be less than the actual molecular weight due to the three dimensional structure of the star polymer.
  • the star polymer of the present invention is derived from about 75 % to about 90 % by mass isoprene and about 10 % to about 25 % by mass butadiene, and greater than 80 % by mass of the butadiene units are incorporated 1,4-addition product.
  • the star polymer of the present invention comprises amorphous butadiene units derived from about 30 to about 80 % by mass 1,2-, and from about 20 to about 70 % by mass 1,4-incorporation of butadiene.
  • the star polymer is derived from isoprene, butadiene, or a mixture thereof, and further contains from about 5 to about 35 % by mass styrene units.
  • the star polymer has a Shear Stability Index (SSI) of from about 1 % to 35 % (30 cycle).
  • SSI Shear Stability Index
  • An example of a commercially available star polymer VI improver having an SSI equal to or less than 35 is Infineum SV200TM, available from Infineum USA L.P. and Infineum UK Ltd.
  • Other examples of commercially available star polymer VI improver having an SSI equal to or less than 35 include Infineum SV250TM, Infineum SV261TM and Infineum SV270TM, also available from Infineum USA L.P. and Infineum UK Ltd.
  • the viscosity index improver is provided in an amount of from 0.01 to 20, preferably 1 to 15, mass % based on the mass of the lubricating oil composition.
  • one or both types of VI improvers used in the practice of the invention can be provided with nitrogen-containing functional groups that impart dispersant capabilities to the VI improver.
  • nitrogen-containing functional groups can be added to a polymeric VI improver by grafting a nitrogen- or hydroxyl- containing moiety, preferably a nitrogen-containing moiety, onto the polymeric backbone of the VI improver (functionalizing).
  • Processes for the grafting of a nitrogen-containing moiety onto a polymer include, for example, contacting the polymer and nitrogen-containing moiety in the presence of a free radical initiator, either neat, or in the presence of a solvent.
  • the free radical initiator may be generated by shearing (as in an extruder) or heating a free radical initiator precursor, such as hydrogen peroxide.
  • the amount of nitrogen-containing grafting monomer will depend, to some extent, on the nature of the substrate polymer and the level of dispersancy required of the grafted polymer. To impart dispersancy characteristics to both star and linear copolymers, the amount of grafted nitrogen-containing monomer is suitably between about 0.4 and about 2.2 mass %, preferably from about 0.5 to about 1.8 mass %, most preferably from about 0.6 to about 1.2 mass %, based on the total weight of grafted polymer.
  • the lubricating oil compositions may be used to lubricate mechanical engine components, particularly in internal combustion engines, e.g. compression-ignited two- or four- stroke reciprocating engines, by adding the composition thereto.
  • the engines may be conventional diesel engines designed to be powered by petroleum diesel; alternatively, the engines may be specifically modified to be powered by 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 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 lubricant during operation of the engine becomes contaminated with biodiesel and decomposition products thereof.
  • the lubricating oil composition 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 biodiesel and/or a decomposition product thereof.
  • the lubricating oil composition may comprise up to 50 mass % of biodiesel and/or a decomposition product thereof, preferably it includes less than 35, more preferably less than 30, mass % of biodiesel and/or a decomposition product thereof.
  • 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 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 - 0.15 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 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.
  • 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 250 to 500 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, 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.
  • 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.
  • Particularly preferred metal detergents are neutral and overbased alkali or alkaline earth metal salicylates having a TBN of from 50 to 450, preferably a TBN of 50 to 250.
  • Highly preferred salicylate detergents include alkaline earth metal salicylates, particularly magnesium and calcium, especially, calcium salicylates.
  • the alkali or alkaline earth metal salicylate detergent 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.
  • 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, in addition to madditive component B.
  • 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.
  • 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 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.
  • a series of 5W-30 multigrade lubricating oil compositions (0.08% P), as detailed in Table 1, were prepared by admixing a Group III base stock with known additives including an overbased calcium sulphonate detergent (TBN 310), an overbased calcium phenate detergent (TBN 150), a non-borated polyisobutylene derived dispersant, ZDDP and an aminic antioxidant.
  • TBN 310 overbased calcium sulphonate detergent
  • TBN 150 overbased calcium phenate detergent
  • ZDDP non-borated polyisobutylene derived dispersant
  • Comparative Lubricant 1 also included an ethylene-propylene copolymer viscosity index improver (LZ-7077TM available from Lubrizol), Lubricant 1 of the invention included an isopropene-butadiene-styrene copolymer star polymer viscosity index improver (Infineum SV261TM available from Infineum UK Ltd) and Lubricant 2 of the invention included an isoprene-styrene block copolymer viscosity index improver (Infineum SV151TM available from Infineum UK Ltd).
  • the oxidation induction times for each of the lubricants was determined in: (a) the absence of biodiesel fuel; and, (b) in the presence of 10 % B50 biodiesel fuel. The results are also detailed in Table 1.

Claims (19)

  1. Verwendung von öllöslichem oder in Öl dispergierbarem Viskositätsindexverbesserer (B), der lineares oder sternförmiges Polymer ist, das von der Polymerisation eines oder mehrerer konjugierter Dienmonomere abgeleitet ist, als Additivkomponente in einer geringeren Menge von 0,01 bis 20 Masse-%, bezogen auf die Masse der Schmierölzusammensetzung, in einer Schmierölzusammensetzung, bei der Schmierung eines kompressionsgezündeten Verbrennungsmotors, der mit Biodiesel betrieben wird, um die Oxidation der Schmierölzusammensetzung während des Betriebs des Motors zu verringern und/oder zu hemmen, und wobei die Schmierölzusammensetzung mit Biodiesel oder einem Zersetzungsprodukt davon während des Betriebs des Motors verunreinigt wird.
  2. Verwendung nach Anspruch 1, bei der das eine oder die mehreren Dienmonomer(e) 1,3-Butadien, Isopren oder Mischungen davon ist bzw. sind.
  3. Verwendung nach Anspruch 1 oder 2, bei der der Viskositätsindexverbesserer mindestens ein sternförmiges, mindestens teilweise hydriertes Polymer ist.
  4. Verwendung nach Anspruch 3, bei der das sternförmige, mindestens teilweise hydrierte Polymer mehrere Arme umfasst, die sich von einem zentralen Kern aus erstrecken, wobei die Arme ein Homopolymer sind, das von einem einzigen der konjugierten Dienmonomere abgeleitet ist oder Copolymer umfassen, das von zwei oder mehreren der konjugierten Dienmonomere abgeleitet ist oder Copolymer umfassen, das von einem oder mehreren der konjugierten Dienmonomere und von vinylaromatischem Kohlenwasserstoffmonomer abgeleitet ist.
  5. Verwendung nach Anspruch 4, bei der die Arme des sternförmigen, mindestens teilweise hydrierten Polymers hydriertes Isopren-Butadien-Copolymer umfassen.
  6. Verwendung nach Anspruch 4, bei der die Arme des sternförmigen, mindestens teilweise hydrierten Polymers hydriertes Styrol-Isopren-Butadien-Copolymer, hydriertes Isopren-Styrol-Copolymer oder Butadien-Styrol-Copolymer umfassen.
  7. Verwendung nach Anspruch 6, bei der das Copolymer der Arme bis zu 35 Masse-%, vorzugsweise bis zu 25 Masse-% Styrolmonomer umfasst.
  8. Verwendung nach Anspruch 3, bei der die Arme des sternförmigen, mindestens teilweise hydrierten Polymers lineares Diblockcopolymer umfassen, das mindestens einen vorrangig von vinylaromatischem Kohlenwasserstoffmonomer abgeleiteten Block und mindestens einen vorrangig von einem oder mehreren der konjugierten Dienmonomere abgeleiteten Block aufweist, und das lineare Diblockcopolymer mindestens teilweise hydriert ist.
  9. Verwendung nach Anspruch 8, bei der das lineare Diblockcopolymer mindestens einen Polystyrolblock und einen Block, der von Isopren, Butadien oder Mischungen davon abgeleitet ist, umfasst und das lineare Diblockcopolymer mindestens teilweise hydriert ist.
  10. Verwendung nach Anspruch 9, bei der das lineare Diblockcopolymer ausgewählt ist aus der Gruppe bestehend aus hydrierten Styrol/Butadien-Diblockcopolymeren, hydrierten Styrol/Isopren-Diblockcopolymeren und hydrierten Styrol/Isopren-Butadien-Diblockcopolymeren.
  11. Verwendung nach Anspruch 10, bei der das lineare Diblockcopolymer hydriertes Styrol/Isopren-Butadien-Diblockcopolymer ist.
  12. Verwendung nach Anspruch 4, bei der die Arme des sternförmigen, mindestens teilweise hydrierten Polymers Homopolymer sind, das von Isoprenmonomeren abgeleitet ist.
  13. Verwendung nach einem der Ansprüche 4 bis 12, bei der der Kern des sternförmigen, mindestens teilweise hydrierten Polymers von polyolefinischem Verknüpfungsmittel abgeleitet ist.
  14. Verwendung nach einem der Ansprüche 1 oder 2, bei der der Viskositätsindexverbesserer lineares Diblockcopolymer ist, das mindestens einen vorrangig von vinylaromatischem Kohlenwasserstoffmonomer abgeleiteten Block und mindestens einen vorrangig von dem einen oder den mehreren konjugierten Dienmonomeren abgeleiteten Block umfasst.
  15. Verwendung nach Anspruch 14, bei der das lineare Diblockcopolymer mindestens einen Polystyrol-Block und einen Block umfasst, der von Isopren, Butadien oder einer Mischung davon abgeleitet ist.
  16. Verwendung nach Anspruch 15, bei der das lineare Diblockcopolymer ausgewählt ist aus der Gruppe bestehend aus hydrierten Styrol/Butadien-Diblockcopolymeren und hydrierten Styrol/Isopren-Diblockcopolymeren.
  17. Verwendung nach einem der vorhergehenden Ansprüche, bei der die Schmierölzusammensetzung in einer größeren Menge von mehr als 50 Masse-% der Schmierölzusammensetzung Öl mit Schmierviskosität umfasst, das Gruppe-III-Basisöl umfasst.
  18. Verwendung nach einem der vorhergehenden Ansprüche, bei der die Schmierölzusammensetzung mit mindestens 0,3 Masse-%, bezogen auf die Gesamtmasse der Schmierölzusammensetzung, Biodiesel oder einem Zersetzungsprodukt davon verunreinigt ist.
  19. Verwendung nach einem der vorhergehenden Ansprüche, bei der die Schmierölzusammensetzung ferner ein oder mehrere Coadditive in einer geringeren Menge von weniger als 50 Masse-% der Schmierölzusammensetzung umfasst, die sich von der öllöslichen oder in Öl dispergierbaren Viskositätsindexverbesserungsadditivkomponente, wie in einem der vorhergehenden Ansprüche definiert, unterscheiden und ausgewählt sind aus aschefreien Dispersionsmitteln, Metalldetergentien, Rostschutzmitteln, Antioxidantien, Pourpoint-Erniedrigern, Antiverschleißmitteln, Reibungsmodifizierungsmitteln, Demulgatoren, Antischaummitteln und Viskositätsmodifizierungsmitteln.
EP10196988.9A 2010-02-23 2010-12-24 Verwendung einer schmierölzusammensetzung Revoked EP2363454B1 (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2055761A2 (de) 2007-10-31 2009-05-06 Chevron Oronite Company LLC Schmierölzusammensetzungen mit einem Biodieselkraftstoff und einem Detergens

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9133413B2 (en) * 2011-12-21 2015-09-15 Infineum International Limited Viscosity index improvers for lubricating oil compositions
ES2657913T3 (es) * 2011-12-21 2018-03-07 Infineum International Limited Lubricación de motor marino
EP2899255B1 (de) * 2013-03-11 2017-08-02 Kuraray Co., Ltd. Ölzusammensetzung mit einem viskositätsindexverbesserer
JPWO2014156306A1 (ja) * 2013-03-28 2017-02-16 Ｊｘエネルギー株式会社 省燃費エンジン油組成物
CN104342231B (zh) * 2013-08-08 2016-12-07 中国石油化工股份有限公司 一种润滑油粘度指数改进剂及其制备方法
CN104419498B (zh) * 2013-08-30 2017-10-17 中国石油天然气股份有限公司 一种具有极性两端的高分子摩擦改进剂
US9879201B2 (en) * 2014-02-28 2018-01-30 Cosmo Oil Lubricants Co., Ltd. Engine oil composition
JP2017507224A (ja) 2014-03-12 2017-03-16 ザ ルブリゾル コーポレイションＴｈｅ Ｌｕｂｒｉｚｏｌ Ｃｏｒｐｏｒａｔｉｏｎ 内燃エンジンを潤滑する方法
JP6544953B2 (ja) * 2014-05-29 2019-07-17 株式会社リコー 画像形成装置及びグリース組成物
US9506009B2 (en) * 2014-05-29 2016-11-29 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
CN105732920B (zh) * 2014-12-11 2018-09-04 中国石油天然气股份有限公司 一种星形氢化苯乙烯双烯共聚物及其制备方法
CN105754055B (zh) * 2014-12-16 2019-01-18 中国石油天然气股份有限公司 一种星形氢化苯乙烯双烯共聚物及其制备方法
EP3505607A1 (de) * 2015-03-24 2019-07-03 Idemitsu Kosan Co., Ltd. Schmiermittelzusammensetzung für einen benzinmotor und verfahren zur herstellung davon
CN106336490B (zh) * 2015-07-15 2018-11-16 中国石油天然气股份有限公司 一种氢化苯乙烯双烯共聚物黏度指数改进剂及其制备方法
US10781394B2 (en) 2016-10-25 2020-09-22 Chevron Oronite Technology B.V. Lubricating oil compositions comprising a biodiesel fuel and a Mannich condensation product
US10344245B2 (en) 2016-10-25 2019-07-09 Chevron Oronite Technology B.V. Lubricating oil compositions comprising a biodiesel fuel and a dispersant
FR3072685B1 (fr) 2017-10-20 2020-11-06 Total Marketing Services Composition pour refroidir et lubrifier un systeme de motorisation d'un vehicule
FR3080383B1 (fr) 2018-04-20 2020-11-20 Total Marketing Services Composition lubrifiante pour moteurs industriels a potentiel fe amplifie
CN109181813B (zh) * 2018-07-31 2021-07-06 沈阳化工研究院有限公司 一种用于润滑油的星形黏度指数改进剂及其制备方法
CN111088091B (zh) * 2018-10-23 2022-03-11 中国石油化工股份有限公司 一种汽油机油组合物及其制备方法
CN111088092B (zh) * 2018-10-23 2022-07-15 中国石油化工股份有限公司 一种重负荷柴油机油组合物及其制备方法
FR3108620B1 (fr) * 2020-03-25 2022-09-09 Total Marketing Services Utilisation de polymère styrène diène hydrogéné pour réduire les émissions de particules

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000027956A1 (en) 1998-11-06 2000-05-18 Shell Internationale Research Maatschappij B.V. Lubricating oil composition
WO2001079399A1 (en) * 2000-04-13 2001-10-25 Ashland Inc. Engine lubricant and additive
US20030119682A1 (en) * 1997-08-27 2003-06-26 Ashland Inc. Lubricant and additive formulation
EP1486557A1 (de) * 2003-06-12 2004-12-15 Infineum International Limited Konzentrate enthaltend Viskositätsindexverbesserer
US20070099808A2 (en) 2003-05-23 2007-05-03 Preservation Sciences, Inc. Compositions and methods for preventing and treating corrosion of metal surfaces
US8999905B2 (en) 2010-10-25 2015-04-07 Afton Chemical Corporation Lubricant additive

Family Cites Families (29)

* 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
NL124842C (de) 1959-08-24
NL255193A (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
US3113986A (en) 1962-01-08 1963-12-10 Hercules Powder Co Ltd Hydrogenation of unsaturated hydrocarbons
NL296137A (de) 1963-08-02 1900-01-01
US3216936A (en) 1964-03-02 1965-11-09 Lubrizol Corp Process of preparing lubricant additives
US3634595A (en) 1969-03-31 1972-01-11 Giorgio Pasquali A generator of harmonic signals with a helical spring
US3670054A (en) 1969-10-29 1972-06-13 Shell Oil Co Block copolymers having reduced solvent sensitivity
US3700633A (en) 1971-05-05 1972-10-24 Shell Oil Co Selectively hydrogenated block copolymers
US3985830B1 (en) 1974-07-15 1998-03-03 Univ Akron Star polymers and process for the preparation thereof
CA1088694A (en) 1975-07-31 1980-10-28 Robert L. Stambaugh Polyolefin grafted with polymers of nitrogen containing monomers and lubricants and fuel compositions containing same
GB1575507A (en) 1976-02-10 1980-09-24 Shell Int Research Hydrogenated star-shaped polymers and oil compositions thereof
US4292414A (en) 1978-08-16 1981-09-29 Asahi Kasei Kogyo Kabushiki Kaisha Process for the preparation of modified block copolymers
US4506056A (en) 1982-06-07 1985-03-19 Gaylord Research Institute Inc. Maleic anhydride-modified polymers and process for preparation thereof
US4849481A (en) * 1987-07-10 1989-07-18 Shell Oil Company Star shaped asymmetric block copolymer of monoalkenyl aromatic hydrocarbon and conjugated diene
IL89210A (en) 1988-02-26 1992-06-21 Exxon Chemical Patents Inc Lubricating oil compositions containing demulsifiers
GB8829896D0 (en) 1988-12-22 1989-02-15 Shell Int Research Preparation of modified star polymers
DE69020099T2 (de) * 1989-10-26 1995-11-16 Shell Int Research Sternförmiges Polymer, seine Herstellung und dieses Polymer enthaltende Schmierölzusammensetzung.
CA2266551C (en) 1996-09-24 2006-05-02 Shell Internationale Research Maatschappij B.V. Dispersant viscosity index improvers
GB9624441D0 (en) * 1996-11-25 1997-01-15 Exxon Research Engineering Co Fuel economy engine oil composition
EP1025138B1 (de) 1997-10-28 2005-03-02 Castrol Limited Verfahren zur herstellung von pfropfcopolymeren
KR100549457B1 (ko) * 1998-02-19 2006-02-06 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 오일 조성물용 스타 중합체 점도지수 증진제
ATE552328T1 (de) * 2005-11-03 2012-04-15 Infineum Int Ltd Lineare diblockcopolymere als verschleissschutzzusatzstoff für schmiermittel der brennkraftmaschinenkurbelgehäuse
JP5806802B2 (ja) * 2007-03-30 2015-11-10 出光興産株式会社 潤滑油組成物
JP5198031B2 (ja) * 2007-10-22 2013-05-15 出光興産株式会社 潤滑油組成物
US7960322B2 (en) * 2007-10-26 2011-06-14 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and an antioxidant
US7838474B2 (en) * 2007-10-31 2010-11-23 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and a detergent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119682A1 (en) * 1997-08-27 2003-06-26 Ashland Inc. Lubricant and additive formulation
WO2000027956A1 (en) 1998-11-06 2000-05-18 Shell Internationale Research Maatschappij B.V. Lubricating oil composition
WO2001079399A1 (en) * 2000-04-13 2001-10-25 Ashland Inc. Engine lubricant and additive
US20070099808A2 (en) 2003-05-23 2007-05-03 Preservation Sciences, Inc. Compositions and methods for preventing and treating corrosion of metal surfaces
EP1486557A1 (de) * 2003-06-12 2004-12-15 Infineum International Limited Konzentrate enthaltend Viskositätsindexverbesserer
US8999905B2 (en) 2010-10-25 2015-04-07 Afton Chemical Corporation Lubricant additive

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Lubricants in the Age of Biodiesel", LUBE-TECH: THE EUROPEAN LUBRICANTS INDUSTRY MAGAZINE, no. 90, April 2009 (2009-04-01), pages 19 - 22, XP055618430
"Standard test Method for Oxidation Induction Time of Lubricating Oils by Pressure Differential Scanning Calorimetry (PDSC)", ASTM D6186-08, January 2009 (2009-01-01), pages 1 - 5, XP009149023

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2055761A2 (de) 2007-10-31 2009-05-06 Chevron Oronite Company LLC Schmierölzusammensetzungen mit einem Biodieselkraftstoff und einem Detergens

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CN102161927B (zh) 2017-06-23
US20110207642A1 (en) 2011-08-25
SG173979A1 (en) 2011-09-29
CA2732190A1 (en) 2011-08-23
JP5781787B2 (ja) 2015-09-24
EP2363454A1 (de) 2011-09-07
CN102161927A (zh) 2011-08-24
CA2732190C (en) 2018-06-19

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