EP3092290B1 - Méthode à lubrifier un moteur à combustion - Google Patents

Méthode à lubrifier un moteur à combustion Download PDF

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Publication number
EP3092290B1
EP3092290B1 EP15701085.1A EP15701085A EP3092290B1 EP 3092290 B1 EP3092290 B1 EP 3092290B1 EP 15701085 A EP15701085 A EP 15701085A EP 3092290 B1 EP3092290 B1 EP 3092290B1
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EP
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Prior art keywords
tbn
lubricating composition
alkaline earth
polyisobutylene succinimide
earth metal
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EP15701085.1A
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German (de)
English (en)
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EP3092290A1 (fr
Inventor
Mary Galic Raguz
John G. Loop
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Lubrizol Corp
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
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    • C10M2215/28—Amides; Imides
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
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    • 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]
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the invention provides a method of lubricating a compression-ignition internal combustion engine with a maximum laden mass over 2,700 kg comprising supplying to the engine a lubricating composition comprising: an oil of lubricating viscosity, a 300 TBN or higher alkaline earth metal sulphonate detergent having a metal ratio of 10 to 40, 0.1 wt % to 4 wt % of a borated polyisobutylene succinimide dispersant, wherein the polyisobutylene from which the borated polyisobutylene succinimide is derived has a number average molecular weight of 550 to 1150, and 0.1 wt % to 6 wt % of a polyisobutylene succinimide, wherein the polyisobutylene from which polyisobutylene succinimide is derived has a number average molecular weight of 1550 to 2500, 0 wt % to 0.2 wt % of a phenolic
  • Phenol-based detergents are known. Among these are phenates based on phenolic monomers, linked with sulfur bridges or alkylene bridges such as methylene linkages derived from formaldehyde.
  • the phenolic monomers themselves are typically substituted with an aliphatic hydrocarbyl group to provide a measure of oil solubility.
  • the hydrocarbyl groups may be alkyl groups, and, historically, dodecylphenol (or propylene tetramer-substituted phenol) has been widely used.
  • An early reference to basic sulfurized polyvalent metal phenates is U.S. Patent 2,680,96, Walker et al., June 1 , 1954 ; see also U.S. Patent 3,372, 1 16, Meinhardt, March 6, 1968 .
  • Alkylphenol based detergents are known for efficacy to provide deposit control, antioxidancy, and assisting in reducing wear.
  • certain alkylphenols and products prepared from them have come under increased scrutiny due to their association as potential endocrine disruptive materials.
  • alkylphenol detergents which are based on oligomers of C 12 alkyl phenols may contain residual monomeric C12 alkyl phenol species.
  • US Patent 7,943,796 (Campbell et al, 4 February 2010 ) discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound, wherein the alkyl group of the alkylhydroxyaromatic compound is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 °C and a final boiling point of no more than about 325 °C as measured by ASTM D86. Also disclosed is a lubricating oil composition containing at least (a) a major amount of an oil of lubricating viscosity and (b) the overbased salt of the oligomerized alkylhydroxyaromatic compound.
  • US Patent 7,435,709 discloses a lubricating oil composition displaying reduced endocrine disruption response, comprising a major amount of an oil of lubricating viscosity; and a detergent comprising an unsulfurized alkali or alkaline earth metal salt of a reaction product of (1) an olefin having at least 10 carbon atoms, wherein greater than 80 mole % of the olefin is a linear C20-C30 n-alpha olefin, wherein less than 10 mole % of the olefin is a linear olefin of less than 20 carbon atoms, and wherein less than 5 mole % of the olefin is branched chain olefin of 18 carbons or less, and (2) a hydroxyaromatic compound.
  • an olefin having at least 10 carbon atoms wherein greater than 80 mole % of the olefin is a linear C20-C30 n-alpha olef
  • US Patent 8,183,192 discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound for use in a lubricating oil composition, wherein the alkyl group of the alkylhydroxyaromatic compound is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 °C and a final boiling point of greater than 325 °C and up to about 400 °C as measured by ASTM D86.
  • a propylene oligomer having an initial boiling point of at least about 195 °C and a final boiling point of greater than 325 °C and up to about 400 °C as measured by ASTM D86, wherein the propylene oligomer contains a distribution of carbon atoms that comprise at least about 50 weight percent of C14 to C20 carbon atoms
  • US Patent 8,207,380 (Campbell et al., 30 October 2008 ) discloses an alkylated hydroxyaromatic compound prepared by reacting at least one hydroxyaromatic compound with a branched olefinic oligomer having from about 20 to about 80 carbon atoms in the presence of a acid catalyst.
  • the alkylated hydroxyaromatic compound has been determined to be substantially free of endocrine disruptive chemicals when the effects were quantified on pubertal development and thyroid function in the intact juvenile female rat.
  • US Patent 8,198,225 discloses an sulfurized metal alkyl phenate compositions having a low alkyl phenol content.
  • the sulfurized metal alkyl phenate compositions can be prepared by reacting a phenol compound of Formula (I) disclosed therein with an aldehyde to form a phenolic resin of Formula (II) disclosed therein and then by reacting the phenolic resin simultaneously with a metal base and a first sulfurizing agent.
  • the sulfurized metal alkyl phenate compositions and the overbased sulfurized metal alkyl phenate compositions disclosed therein may be used as detergents for formulating lubricating oil compositions.
  • the lubricating oil compositions disclosed therein have a reduced amount of the free phenol compound and a salt thereof
  • US Patent application 2011/0124539 discloses an overbased, sulfurized salt of at least one alkylated hydroxyaromatic compound, wherein the alkyl substituent of the hydroxyaromatic compound is a residue of at least one isomerized olefin having from about 15 to about 99 wt. % branching is disclosed.
  • the overbased, sulfurized salt of at least one alkylated hydroxyaromatic compound is produced by the process comprising: (a) alkylating at least one hydroxyaromatic compound with at least one isomerized olefin having from about 15 to about 99 wt.
  • % branching obtained by isomerizing at least one normal alpha olefin having from about 10 to about 40 carbon atoms, to provide at least one alkylated hydroxyaromatic compound; (b) neutralizing and sulfurizing the alkylated hydroxyaromatic compound in any order to provide at least one neutralized, sulfurized alkylated hydroxyaromatic compound; and (c) overbasing the at least one neutralized, sulfurized alkylated hydroxyaromatic compound
  • US Patent 6,004,910 discloses a heavy duty diesel engine lubricant comprising a boronated succinimide dispersant, a boron free succinimide dispersant, a sulfonate detergent and a magnesium salt of an oil soluble organic acid.
  • the present invention allows for an internal combustion engine (typically a compression ignited engine) to have at least one of reduced soot, reduced deposit formation, reduced wear and improved cleanliness.
  • an internal combustion engine typically a compression ignited engine
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of' and “consisting of,” where “consisting of' excludes any element or step not specified and “consisting essentially of' permits the inclusion of additional un-recited elements or steps that do not materially affect the basic, essential and novel characteristics of the composition or method under consideration.
  • compression ignited internal combustion engine is intended to encompass internal combustion engines that has at least in part compression ignition.
  • the invention is intended to encompass a method of lubricating a compression ignited internal combustion engine, as well as spark assisted compression ignited internal combustion engines.
  • soap means the surfactant portion of a detergent and does not include a metal base, such as calcium carbonate.
  • the soap term may also be referred to as a detergent substrate.
  • the sulphonate detergents described herein, the soap or substrate is a neutral salt of an alkylbenzenesulphonic acid.
  • the present invention provides a method of lubricating a compression-ignition internal combustion engine with a maximum laden mass over 2,700 kg comprising supplying to the engine a lubricating composition comprising:
  • Described is a method of lubricating a compression-ignition internal combustion engine with a maximum laden mass over 2,700 kg comprising supplying to the engine a lubricating composition comprising:
  • Described is a method of lubricating a compression-ignition internal combustion engine with a maximum laden mass over 2,700 kg comprising supplying to the engine a lubricating composition comprising:
  • Described is a method of lubricating a compression-ignition internal combustion engine with a maximum laden mass over 2,700 kg comprising supplying to the engine a lubricating composition comprising:
  • the lubricating composition comprises 0 wt % of a phenolic based detergent.
  • the phenolic based detergent may be a phenate.
  • the phenolic based detergent may be chosen from a phenate, and a salycilate.
  • the phenolic based detergent may be chosen from a phenate, a salycilate, and a salixarate.
  • the phenate may be a non-sulphur containing phenate, sulphur containing phenate, or a "hybrid" detergent formed with mixed surfactant system, wherein the hybrid is a mixed phenate-salicylate, a sulphonate-phenate, or a sulphonate-phenate-salicylate.
  • the lubricating composition comprises 0 wt % of the phenolic based detergent. In this embodiment the lubricating composition comprises only sulphonate detergents.
  • the laden mass (sometimes referred to as gross vehicle weight rating (GVWR)) may be over 2,700 kg (or 6,000 USA pounds) 2,900 kg, or over 3,00 kg, or over 3,300 kg, or over 3,500 kg, or over 3,700 kg, or over 3,900 kg (or 8,500 USA pounds).
  • GVWR gross vehicle weight rating
  • the upper limit on the laden mass or GVWR is set by national government and may be 10,000 kg, or 9,000 kg, or 8,000 kg, or 7,500 kg.
  • Heavy duty diesel engines are noted to be limited to all motor vehicles with a “technically permissible maximum laden mass” over 3,500 kg, equipped with compression ignition engines or positive ignition natural gas (NG) or LPG engines.
  • NG positive ignition natural gas
  • LPG low-duty truck
  • the internal combustion engine is a heavy duty diesel compression ignited (or spark assisted compression ignited) internal combustion engine.
  • the invention provides for the use of a lubricating composition disclosed herein to provide at least one of reduced soot, reduced deposit formation, reduced wear and improved cleanliness in a compression ignited internal combustion engine (typically a diesel internal combustion engine).
  • a compression ignited internal combustion engine typically a diesel internal combustion engine.
  • the present invention provides a method for lubricating an internal combustion engine and a use as disclosed above.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704 , paragraphs [0054] to [0056] (a similar disclosure is provided in US Patent Application 2010/197536 , see [0072] to [0073]).
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • Oils of lubricating viscosity may also be defined as specified in April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories”.
  • the API Guidelines are also summarised in US Patent US 7,285,516 (see column 11, line 64 to column 12, line 10).
  • the oil of lubricating viscosity may be an API Group I to IV mineral oil, an ester or a synthetic oil, or mixtures thereof. In one embodiment the oil of lubricating viscosity may be an API Group II, Group III, Group IV mineral oil, an ester or a synthetic oil, or mixtures thereof.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the additives of the invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight. Typically the lubricating composition of the invention comprises at least 50 wt %, or at least 60 wt %, or at least 70 wt %, or at least 80 wt % of an oil of lubricating viscosity.
  • Overbased materials otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterized by a metal content in of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a calcium chloride, acetic acid, phenol or alcohol.
  • the acidic organic material will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil.
  • the amount of "excess" metal is commonly expressed in terms of metal ratio.
  • metal ratio is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 3.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • the lubricating composition disclosed herein comprises at least one calcium sulphonate detergent described herein.
  • the lubricating composition comprises at least one or at least two other sulphonate detergents.
  • the sulphonate detergents of the invention are known to a person skilled in the art.
  • the lubricating composition further comprises another sulphonate detergent, typically a magnesium, sodium or zinc overbased sulphonate.
  • another sulphonate detergent typically a magnesium, sodium or zinc overbased sulphonate.
  • any additional sulphonate detergent may be a magnesium or sodium sulphonate detergent, with magnesium sulphonate the more typical.
  • the lubricating composition comprises a 300 TBN or higher alkaline earth metal sulphonate detergent having a metal ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal sulphonate detergent having a metal ratio of 1 to 5.
  • the lubricating composition comprises a300 TBN or higher alkaline earth metal sulphonate detergent comprises a magnesium sulphonate detergent having a metal ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal sulphonate detergent comprising a calcium sulphonate detergent having a metal ratio of 1 to 5.
  • the lubricating composition comprises 300 TBN or higher alkaline earth metal sulphonate detergent comprising a mixture of a calcium sulphonate detergent having a metal ratio of 10 to 40, and a magnesium sulphonate detergent having a metal ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal sulphonate detergent comprises a calcium sulphonate detergent having a metal ratio of 1 to 5.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent and the 80 TBN or lower alkaline earth metal sulphonate detergent may be prepared from the same or different hydrocarbyl-substituted sulphonic acids.
  • the hydrocarbyl-substituted sulphonic acids are alkyl-substituted sulphonic acids.
  • the sulphonate may be prepared from a mono- or di- hydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35 or 9 to 30 carbon atoms.
  • the hydrocarbyl group may be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms.
  • a suitable alkyl group include branched and/or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl or mixtures thereof.
  • the hydrocarbyl-substituted sulphonic acid may include polypropene benzenesulphonic acid and C 16 -C 24 alkyl benzenesulphonic acid, or mixtures thereof.
  • the 300 TBN sulphonate detergent may be a predominantly linear alkylbenzene sulphonate detergent having a metal ratio of having a metal ratio of 10 to 40 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919 ).
  • the predominantly linear alkylbenzene sulphonate detergent may be particularly useful for assisting in improving fuel economy.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent has a metal ratio of 12 to 30, or 12 to 22, or 16 to 20, or 10 to 20, or 20 to 30, or 22 to 25 mg KOH/g. In one embodiment the 300 TBN metal ratio may be 16 to 20, and in another embodiment 22 to 25.
  • the calcium sulphonate detergent having a metal ratio of 10 to 40 may have a TBN of 350 to 500, or 375 to 425 mg KOH/g.
  • the calcium sulphonate may have a TBN ranging from 350 to 500 and a metal ratio of 20 to 30, or may have a TBN of 375 to 425 mg KOH/g; and a metal ratio of 22 to 25.
  • a calcium sulphonate detergent may have TBN of 1 to 80, or 1 to 75, typically 2 to 50 mg KOH/g, or 5 to 35 mg KOH/g.
  • the calcium sulphonate detergent having a metal ratio of 1 to 5 may have a TBN of 1 to 80, or 2 to 40, or 5 to 35 mg KOH/g. Typically the calcium sulphonate detergent having a metal ratio of 1 to 5 has a TBN of 5 to 35 mg KOH/g.
  • the lubricating composition comprises a calcium sulphonate detergent having a metal ratio of 10 to 40, and a calcium sulphonate detergent having a metal ratio of 1 to 5.
  • the lubricating composition comprises a calcium sulphonate detergent having a metal ratio of 10 to 40, a calcium sulphonate detergent having a metal ratio of 1 to 5, and a magnesium sulphonate detergent having a metal ratio of 12 to 40.
  • the magnesium sulphonate detergent may have a TBN of 300 to 500, or 350 to 425 mg KOH/g; and a metal ratio of 12 to 40, or 14 to 25.
  • the magnesium sulphonate may have the same or different hydrocarbyl-substituted sulphonic acids, and are defined the same as described above for calcium sulphonate detergents.
  • the other sulphonate (typically magnesium sulphonate) detergent may be present in an amount such as 0.01 wt % to 0.5 wt %, or 0.2 wt % to 0.3 wt %.
  • the lubricating composition consists of only two (or three) detergents i.e., the two calcium sulphonate detergents, and optionally a magnesium sulphonate detergent which is present or absent in different embodiment.
  • At least two of the sulphonate detergents are calcium sulphonate detergents.
  • the 80 TBN or lower alkaline earth metal sulphonate detergent may be a calcium sulphonate, or the 300 TBN or higher alkaline earth metal sulphonate detergent may be a calcium or magnesium sulphonate.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent comprises a calcium sulphonate detergent having a metal ratio of 10 to 40
  • the 80 TBN or lower alkaline earth metal sulphonate detergent comprises a calcium sulphonate detergent having a metal ratio of 1 to 5.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent comprises a magnesium sulphonate detergent having a metal ratio of 10 to 40
  • the 80 TBN or lower alkaline earth metal sulphonate detergent comprises a calcium sulphonate detergent having a metal ratio of 1 to 5.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent comprises a mixture of a calcium sulphonate detergent having a metal ratio of 10 to 40, and a magnesium sulphonate detergent having a metal ratio of 10 to 40, and the 80 TBN or lower alkaline earth metal sulphonate detergent comprises a calcium sulphonate detergent having a metal ratio of 1 to 5.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent mixture comprise calcium sulphonate detergent having a metal ratio of 16 to 20, and the magnesium sulphonate detergent having a metal ratio of 12 to 40.
  • the 300 TBN or higher alkaline earth metal sulphonate detergent mixture comprise calcium sulphonate detergent having a metal ratio of 22 to 25, and the magnesium sulphonate detergent having a metal ratio of 14 to 25.
  • the lubricating composition comprises:
  • the succinimide dispersants of both the borated polyisobutylene succinimide and the polyisobutylene succinimide may be derived from an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine. In one embodiment the aliphatic polyamine may be chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the borated polyisobutylene succinimide may be prepared borated using a variety of agents including boric acid (for example, metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7 ), boric oxide, or boron trioxide.
  • boric acid for example, metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7
  • boric oxide for example, metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7
  • boric oxide for example, metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7
  • boron trioxide for example, metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4
  • the borated dispersant may be prepared by blending the boron compound and the N-substituted long chain alkenyl succinimides and heating them at a suitable temperature, such as, 80 °C to 250 °C, or 90 °C to 230 °C, or 100 °C to 210 °C, until the desired reaction has occurred.
  • the molar ratio of the boron compounds to the N-substituted long chain alkenyl succinimides may have ranges including 10:1 to 1:4, or 4:1 to 1:3, or 1:2.
  • An inert liquid may be used in performing the reaction.
  • the liquid may include toluene, xylene, chlorobenzene, dimethylformamide or mixtures thereof.
  • the borated polyisobutylene succinimide dispersant may be present at 0.1 to 2 wt %, or 0.2 wt % to 1 wt %.
  • Both the borated polyisobutylene succinimide and the polyisobutylene succinimide may have a TBN on an oil free basis of 40 or more, 70 or more, or 85 or more, such as 50 to 130, or 80 to 120, or 90 to 115.
  • the total amount of dispersant (from the combination of borated polyisobutylene succinimide and the polyisobutylene succinimide may be present at 2.6 wt % to 8 wt %, or 3.2 wt % to 6 wt %.
  • polyisobutylene succinimide present at. 2.5 wt % to 6 wt %, or 3 wt % to 5 wt %.
  • the polyisobutylene succinimide is present in an amount greater than the borated polyisobutylene succinimide.
  • the borated polyisobutylene succinimide may comprise less than 50 wt %, or less than 30 wt % of dispersant present.
  • the borated polyisobutylene succinimide may contribute 5 wt % to 25 wt % of dispersant present.
  • the polyisobutylene succinimide may contribute more than 50 wt %, or more than 70 wt % of dispersant present.
  • the polyisobutylene succinimide may contribute 75 wt % to 95 wt % of dispersant present.
  • the polyisobutylene succinimide dispersant may comprise a polyisobutylene succinimide, wherein the polyisobutylene from which polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000, or 750 to 3000 or 1550 to 2500.
  • Both the borated polyisobutylene succinimide and the polyisobutylene succinimide may have a carbonyl to nitrogen ratio of 1:1 to 1:5, or 1:1 to 1:4, or 1:1.3 to 3: or 1:1.5 to 1:2, or 1:1.4 to 1:0.6.
  • the lubricating composition of the invention in one embodiment further contains a dispersant viscosity modifier.
  • the dispersant viscosity modifier may be present at 0.05 wt % to 1.5 wt %, or 0.1 wt % to 1 wt %, or 0.1 to 0.5 wt %.
  • the dispersant viscosity modifier may include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalised with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalised with an amine, or styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication WO2006/015130 or U.S. Patents 4,863,623 ; 6,107,257 ; 6,107,258 ; 6,117,825 ; and US 7,790,661 . In one embodiment the dispersant viscosity modifier may include those described in U.S. Patent 4,863,623 (see column 2, line 15 to column 3, line 52) or in International Publication WO2006/015130 (see page 2, paragraph [0008] and preparative examples are described paragraphs [0065] to [0073]).
  • the dispersant viscosity modifier comprises an olefin copolymer further functionalised with a dispersant amine group.
  • the olefin copolymer is an ethylene-propylene copolymer.
  • the olefin copolymer has a number average molecular weight of 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.
  • the dispersant amine group may be prepared/derived from reacting the olefin copolymer (typically, an ethylene-propylene copolymer) with an acylating agent (typically maleic anhydride) and an aromatic amine having a primary or secondary amino group.
  • the dispersant viscosity modifier may be an ethylene-propylene copolymer acylated with maleic anhydride and reacted with an aromatic amine.
  • the formation of a dispersant viscosity modifier is well known in the art.
  • the dispersant viscosity modifier may include for instance those described in U.S. Patent US 7,790,661 column 2, line 48 to column 10, line 38.
  • the dispersant viscosity modifier may be prepared by grafting of an olefinic carboxylic acid acylating agent onto a polymer of 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of C 3-10 ⁇ -monoolefin, and from 0 to 15 mole percent of non-conjugated diene or triene, said polymer having an average molecular weight ranging from 5000 to 500,000, and further reacting said grafted polymer with an amine (typically an aromatic amine).
  • an amine typically an aromatic amine
  • the aromatic amine of the dispersant viscosity modifier may also include those which can be represented by the general structure NH 2 -Ar or T-NH-Ar, where T may be alkyl or aromatic, Ar is an aromatic group, including nitrogen-containing or amino-substituted aromatic groups and Ar groups including any of the following structures: as well as multiple non-condensed or linked aromatic rings.
  • Aromatic amines include those amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
  • the amines may be monoamines or polyamines.
  • the aromatic ring will typically be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
  • aromatic amines examples include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, di-(para-methylphenyl)amine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, naphthylamine, 4-(4-nitrophenylazo)aniline (disperse orange 3), sulphamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide (N-(4-aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-phenyl)-benzamide, various benzylamines such as 2,5-dimethoxybenzylamine, 4-phenylazoaniline, and substituted versions of these.
  • N-alkylanilines such as N-methylaniline and N-butylaniline
  • aromatic amines include amino-substituted aromatic compounds and amines in which the amine nitrogen is a part of an aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline.
  • aromatic amines such as 2-aminobenzimidazole, which contains one secondary amino group attached directly to the aromatic ring and a primary amino group attached to the imidazole ring.
  • Other amines include N-(4-anilinophenyl)-3-aminobutanamide or 3-amino propyl imidazole.
  • Yet other amines include 2,5-dimethoxybenzylamine.
  • Additional aromatic amines and related compounds are disclosed in U.S. Patent 6,107,257 and 6,107,258 ; some of these include aminocarbazoles, benzoimidazoles, aminoindoles, aminopyrroles, amino-indazolinones, amino-perimidines, mercaptotriazoles, aminophenothiazines, aminopyridines, aminopyrazines, aminopyrimidines, pyridines, pyrazines, pyrimidines, amino-thiadiazoles, aminothiothiadiazoles, and aminobenzotriaozles.
  • Suitable amines include 3-amino-N-(4-anilinophenyl)-N-isopropyl butanamide, and N-(4-anilinophenyl)-3- ⁇ (3-aminopropyl)-(cocoalkyl)amino ⁇ butanamide.
  • Other aromatic amines which can be used include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include materials of the general structure: and isomeric variations thereof, where R viii and R ix are independently alkyl or alkoxy groups such as methyl, methoxy, or ethoxy. In one instance, R viii and R ix are both -OCH 3 and the material is known as Fast Blue RR [CAS# 6268-05-9].
  • R ix is -OCH 3 and R viii is -CH 3 , and the material is known as Fast Violet B [99-21-8]. When both R viii and R ix are ethoxy, the material is Fast Blue BB [120-00-3].
  • U.S. Patent 5,744,429 discloses other aromatic amine compounds, particularly aminoalkylphenothiazines. N-aromatic substituted acid amide compounds, such as those disclosed in U.S. Patent Application 2003/0030033 A1 , may also be used for the purposes of this invention. Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxyclic compound, that is, the nitrogen is not sp 2 hybridized within an aromatic ring.
  • the aromatic amine may also comprise an amine formed by reacting an aldehyde with 4-aminodiphenylamine.
  • the resultant amine may be described as an alkylene coupled amine having at least 4 aromatic groups, at least one -NH 2 functional group, and at least 2 secondary or tertiary amino groups.
  • the aldehyde may be aliphatic, alicyclic or aromatic.
  • the aliphatic aldehyde may be linear or branched.
  • Examples of a suitable aromatic aldehyde include benzaldehyde or o-vanillin.
  • Examples of an aliphatic aldehyde include formaldehyde (or a reactive equivalent thereof such as formalin or paraformaldehyde), ethanal or propanal.
  • the aldehyde may be formaldehyde or benzaldehyde.
  • this aromatic amine may also be prepared by the methodology described in Berichte der Deutschen Chemischen Deutschen Chemischen Deutschen Chemischen
  • the aromatic amine includes 4-aminodiphenylamine, aldehyde (typically formaldehyde) coupled 4-aminodiphenylamine, nitro-aniline (3- nitro-aniline), disperse orange-3 (DO3), or mixtures thereof.
  • a lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described herein below).
  • the lubricating composition of the invention optionally comprises other performance additives.
  • the other performance additives include at least one of metal deactivators, viscosity modifiers, friction modifiers, antiwear agents, corrosion inhibitors, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
  • fully-formulated lubricating oil will contain one or more of these performance additives.
  • the lubricating composition in a further embodiment comprises an antioxidant, wherein the antioxidant comprises a phenolic or an aminic antioxidant or mixtures thereof.
  • the antioxidants include diarylamines, alkylated diarylamines, hindered phenols, or mixtures thereof. When present the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt % of the lubricating composition.
  • the diarylamine or alkylated diarylamine may be a phenyl- ⁇ -naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof.
  • the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105 .
  • the friction modifier may be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides.
  • the friction modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.
  • fatty alkyl or "fatty” in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
  • Suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products
  • Friction modifiers may also encompass materials such as sulphurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • the lubricating composition optionally further includes at least one antiwear agent.
  • suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulphurised olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides.
  • the antiwear agent may in one embodiment include a tartrate, or tartrimide as disclosed in International Publication WO 2006/044411 or Canadian Patent CA 1 183 125 .
  • the tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8.
  • the antiwear agent may in one embodiment include a citrate as is disclosed in US Patent Application 20050198894 .
  • oil-soluble titanium compounds as disclosed in US 7,727,943 and US2006/0014651 .
  • the oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
  • the oil soluble titanium compound is a titanium (IV) alkoxide.
  • the titanium alkoxide is formed from a monohydric alcohol, a polyol or mixtures thereof.
  • the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
  • the titanium alkoxide is titanium (IV) isopropoxide.
  • the titanium alkoxide is titanium (IV) 2-ethylhexoxide.
  • the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol.
  • the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic acid.
  • the oil soluble titanium compound is a titanium carboxylate.
  • the titanium (IV) carboxylate is titanium neodecanoate.
  • the lubricating composition may in one embodiment further include a phosphorus-containing antiwear agent.
  • the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof.
  • Zinc dialkyldithiophosphates are known in the art.
  • the antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricating composition.
  • EP agents include chlorinated wax; sulphurised olefins (such as sulphurised isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, organic sulphides and polysulphides such as dibenzyl-disulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl
  • Foam inhibitors that may be useful in the compositions of the invention include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • Pour point depressants that may be useful in the compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.
  • Metal deactivators include derivatives of benzotriazoles (typically tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles.
  • the metal deactivators may also be described as corrosion inhibitors.
  • Seal swell agents include sulfolene derivatives Exxon Necton-37TM (FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
  • the internal combustion engine may be a 4-stroke engine.
  • the internal combustion engine may or may not have an Exhaust Gas Recirculation system.
  • the internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
  • DPF diesel particulate filters
  • SCR selective catalytic reduction
  • the lubricating composition may be characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterised as having at least one of (i) a sulphur content of 0.2 wt % to 0.4 wt % or less, (ii) a phosphorus content of 0.08 wt % to 0.15 wt %, and (iii) a sulphated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterised as having a sulphated ash content of 0.5 wt % to 1.2 wt %.
  • the lubricating composition may have a total sulphated ash content of 1.2 wt % or less.
  • the sulphur content of the lubricating composition may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %.
  • the phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less.
  • the phosphorus content may be 0.04 wt % to 0.12 wt %.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulphated ash content may be 0.3 wt % to 1.2 wt %, or 0.5 wt % to 1.1 wt % of the lubricating composition. In one embodiment the sulphated ash content may be 0.5 wt % to 1.1 wt % of the lubricating composition.
  • the lubricating composition may be characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.15 wt % or less, and (iii) a sulphated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterised as having at least one of (i) a sulphur content of 0.2 wt % to 0.4 wt % or less, (ii) a phosphorus content of 0.08 wt % to 0.15 wt %, and (iii) a sulphated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterised as having a sulphated ash content of 0.5 wt % to 1.2 wt %.
  • TBN values are (total base number) measured by the methodology described in ASTM D4739 (buffer).
  • the lubricating composition may be characterized as having a total base number (TBN) content of at least 5 mg KOH/g.
  • the lubricating composition may be characterized as having a total base number (TBN) content of 6 to 13 mg KOH/g, or 7 to 12 mg KOH/g.
  • TBN total base number
  • the lubricating composition may have a SAE viscosity grade of XW-Y, wherein X may be 0, 5, 10, or 15; and Y may be 20, 30, or 40.
  • the internal combustion engine disclosed herein may have a steel surface on a cylinder bore, cylinder block, or piston ring.
  • the internal combustion engine may have a surface of steel, or an aluminium alloy, or an aluminium composite.
  • the compression-ignition internal combustion engine has a maximum laden mass over 3,500 kg.
  • a series of lubricating compositions are prepared according to Table 1 below. Each composition is formulated to deliver about 1% by weight sulfated ash (ASTM D874) and to have an overall TBN of about 10 (ASTM D2896).
  • Succinated polyisobutylene (the polyisobutylene has a vinylidene content of less than 25 wt %, and a number average molecular weight of about 2200), aminated with polyaromatic amine 5.
  • OCP ethylene-propylene copolymer having a number average molecular weight of about 8000
  • DVM booster aminated with aromatic amine 6.
  • Other additives include low levels of corrosion inhibitors, ashless TBN booster, and anti-foam agents 8. No ashless TBN booster
  • the lubricating compositions are evaluated for both durability (i.e. anti-wear) and cleanliness (i.e. deposit control).
  • Durability is measured in the GM 6.5L Roller Follower Wear Test (RFWT), an industry standard wear test for measuring wear in diesel engines where soot accumulates in the lubricant.
  • Deposit control is evaluated in the Caterpillar IN (CAT IN) single cylinder engine test, an industry standard test for measuring the ability of diesel lubricants to control oil consumption and prevent/reduce piston deposits especially top groove fill and top land heavy carbon. The results of these tests are summarized in Table 2 below. It is known that lower viscosity grade oils (e.g.
  • the data demonstrates that the formulation with the combination of low and high metal ratio sulphonates and ashless dispersant reduced wear without having a negative impact on deposit control.
  • the results obtained indicate that the lubricating composition disclosed herein provides at least one of soot, reduced deposit formation, reduced wear and improved cleanliness to a heavy duty diesel engine.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.
  • the number average molecular weight of the dispersant viscosity modifier and viscosity modifier has been determined using known methods, such as GPC analysis using polystyrene standards.
  • Methods for determining molecular weights of polymers are well known. The methods are described for instance: (i) P.J. Flory, “Principles of Polymer Chemistry", Cornell University Press 91953), Chapter VII, pp 266-315 ; or (ii) " Macromolecules, an Introduction to Polymer Science", F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312 .

Claims (17)

  1. Procédé de lubrification d'un moteur à combustion interne à auto-allumage avec une masse de charge maximale supérieure à 2 700 kg comprenant la distribution au moteur d'une composition lubrifiante comprenant :
    une huile de viscosité lubrifiante,
    un détergent à base de sulfonate de métal alcalino-terreux de 300 TNB ou plus ayant un rapport de métal de 10 à 40,
    0,1 % en poids à 4 % en poids d'un dispersant de polyisobutylène-succinimide boré, le polyisobutylène à partir duquel le polyisobutylène-succinimide boré est dérivé ayant un poids moléculaire moyen en nombre de 550 à 1150, et
    0,1 % en poids à 6 % en poids d'un polyisobutylène-succinimide, le polyisobutylène à partir duquel le polyisobutylène-succinimide est dérivé ayant un poids moléculaire moyen en nombre de 1550 à 2500,
    0 % en poids d'un détergent à base de phénolique,
    la quantité totale de savon délivrée par le sulfonate de métal alcalino-terreux de 300 TBN ou plus est de 0,4 à 1 % en poids de la composition lubrifiante, et
    la composition lubrifiante a une teneur en cendres sulfuriques de pas plus de 1,5 % en poids, le TBN étant mesuré selon l'ASTM D2896-11.
  2. Procédé selon la revendication 1, dans lequel la composition lubrifiante est caractérisée en ce qu'elle a (i) une teneur en soufre de 0,5 % en poids ou moins, (ii) une teneur en phosphore de 0,1 % en poids ou moins, et (iii) une teneur en cendres sulfuriques de 0,5 % en poids à 1,5 % en poids ou 0,5 % en poids à 1,2 % en poids.
  3. Procédé selon la revendication 1, dans lequel la composition lubrifiante est caractérisée en ce qu'elle a au moins l'une parmi (i) une teneur en soufre de 0,2 % en poids à 0,4 % en poids, (ii) une teneur en phosphore de 0,08 % en poids à 0,15 % en poids, et (iii) une teneur en cendres sulfuriques de 0,5 % en poids à 1,5 % en poids ou 0,5 % en poids à 1,2 % en poids.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition lubrifiante est caractérisée en ce qu'elle a une teneur en indice de base total (TBN) d'au moins 5 mg KOH/g ou 7 à 10 mg KOH/g, le TBN étant mesuré selon l'ASTM D2896-11.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le détergent à base de sulfonate de métal alcalino-terreux de 300 TBN ou plus est un détergent à base de sulfonate de calcium et la quantité totale de savon délivrée par le détergent à base de sulfonate de calcium est de 0,5 à 0,8 % en poids de la composition lubrifiante.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition lubrifiante comprend en outre un détergent à base de sulfonate de métal alcalino-terreux de 80 TBN ou moins ayant un rapport métallique de 1 à 5.
  7. Procédé selon la revendication 6, dans lequel le rapport du détergent à base de sulfonate de métal alcalino-terreux de 300 TBN ou plus au détergent à base de sulfonate de métal alcalino-terreux de 80 TBN ou moins est de 80:20 à 20:80, ou 70:30 à 30:70, ou 65:35 à 35:65.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel le rapport métallique du détergent à base de sulfonate de métal alcalino-terreux de 300 TBN ou plus est de 20 à 30, ou de 22 à 25.
  9. Procédé selon l'une quelconque des revendications précédentes 6 à 8, dans lequel le détergent à base de sulfonate de métal alcalino-terreux de 80 TBN ou moins a un rapport métallique de 1 à 3, ou 1 à 2, ou 1 à 1,5.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition lubrifiante comprend en outre un antioxydant, l'antioxydant comprenant un antioxydant phénolique ou aminé ou des mélanges de ceux-ci, et dans lequel l'antioxydant est présent à 0,1 % en poids à 3 % en poids, ou 0,5 % en poids à 2,75 % en poids, ou 1 % en poids à 2,5 % en poids.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polyisobutylène-succinimide est présent à 2,5 % en poids à 6 % en poids, ou 3 % en poids à 5 % en poids.
  12. Procédé selon la revendication 11, dans lequel le polyisobutylène à partir duquel le polyisobutylène-succinimide est dérivé a un poids moléculaire moyen en nombre de 350 à 5000, ou 750 à 3000 ou 1550 à 2500 et un rapport du carbonyle à l'azote de 1:1 à 1:5, ou 1:1 à 1:4, ou 1:1,3 à 3 : ou 1:1,5 à 1:2, ou 1:1,4 à 1:0,6.
  13. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polyisobutylène-succinimide boré est présent à 0,1 à 2 % en poids, ou 0,2 % en poids à 1 % en poids.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polyisobutylène-succinimide est présent en une quantité supérieure au polyisobutylène-succinimide boré.
  15. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polyisobutylène-succinimide boré contribue à 5 % en poids à 25 % en poids du dispersant présent ; et le polyisobutylène-succinimide contribue à 75 % en poids à 95 % en poids du dispersant présent.
  16. Procédé selon l'une quelconque des revendications précédentes, dans lequel le moteur à combustion interne comporte une surface d'acier, ou un alliage d'aluminium, ou un composite d'aluminium.
  17. Procédé selon l'une quelconque des revendications précédentes, dans lequel le moteur à combustion interne comporte une surface en acier sur un alésage de cylindre, un bloc-cylindres ou un segment de piston.
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US20190292481A1 (en) 2019-09-26
CA2936282A1 (fr) 2015-07-16
SG11201605522SA (en) 2016-08-30
US20160326453A1 (en) 2016-11-10
CA2936282C (fr) 2022-06-07
WO2015106090A1 (fr) 2015-07-16

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