EP3268456A1 - Method of lubricating an internal combustion engine - Google Patents

Method of lubricating an internal combustion engine

Info

Publication number
EP3268456A1
EP3268456A1 EP16710605.3A EP16710605A EP3268456A1 EP 3268456 A1 EP3268456 A1 EP 3268456A1 EP 16710605 A EP16710605 A EP 16710605A EP 3268456 A1 EP3268456 A1 EP 3268456A1
Authority
EP
European Patent Office
Prior art keywords
group
lubricating composition
antioxidant
amine
lubricating
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.)
Withdrawn
Application number
EP16710605.3A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alexandra Mayhew
Robert I. WILBY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP3268456A1 publication Critical patent/EP3268456A1/en
Withdrawn legal-status Critical Current

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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
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2215/02—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
    • C10M2215/065—Phenyl-Naphthyl 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
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/062—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C10N2030/041—Soot induced viscosity control
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Definitions

  • the disclosed technology provides 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 sulfonate detergent having a metal ratio of 10 to 40, an alkaline earth metal sulfonate detergent having a metal ratio of 3 to 9, and a TBN of 81 to 180 mg KOH/g, wherein the sulfonate detergents provide a total amount of sulfonate substrate of 1 wt % to 3 wt % of the lubricating composition, 0.1 to
  • the lubricating composition has a sulfated ash content of 0.5 wt % to not more than 1.5 wt %, and the lubricating composition has a TBN of 6.5 to 15 mg KOH/g.
  • 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 C12 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 are 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
  • the lubricating composition may be used in diesel engines that operate under severe conditions and loads while reducing the impact of soot and soot-related wear as well as cleanliness and deposits.
  • the lubricating composition may have at least one of enhanced deposit control, increased wear control (i.e., reduced wear) or copper or lead Pb corrosion control.
  • the disclosed technology 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 amounts of additives present in the lubricating composition disclosed herein are quoted on an oil free basis, i.e., amount of actives, unless otherwise indicated.
  • 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 disclosed technology 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 sulfonate detergents described herein, the soap or substrate may be a neutral salt of an alkylbenzenesulfonic acid.
  • the disclosed technology 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 alkaline earth metal sulfonate detergent having a metal ratio of 3 to 9, and a
  • TBN 81 to 180 mg KOH/g (as measured by ASTM D2896-11), wherein the sulfonate detergents provide a total amount of sulfonate substrate of 0.8 wt % to 3 wt %, or 0.9 wt % to 3 wt %, or 1 wt % to 3 wt % of the lubricating composition,
  • antioxidant 0.1 to 1.2 wt % of antioxidant, wherein at least 20 wt % of the antioxidant may be a phenolic antioxidant,
  • a borated compound present in an amount to deliver 25 ppm to 300 ppm of boron and the borated compound may be chosen from
  • the lubricating composition has a sulfated ash content of 0.4 wt % to 2 wt %, or 0.5 wt % to 1.8 wt %, or 0.5 wt % to not more than 1.5 wt %, and
  • the lubricating composition has a TBN of 6.5 to 15 mg KOH/g (as measured by ASTM D2896-11).
  • the disclosed technology relates to 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,
  • an alkaline earth metal sulfonate detergent having a metal ratio of 3 to 9, and a TBN of 81 to 180 mg KOH/g (as measured by ASTM D2896-11),
  • the sulfonate detergents provide a total amount of sulfonate substrate of 0.8 wt % to 3 wt %, or 0.9 wt % to 3 wt %, or 1 wt % to 3 wt % of the lubricating composition,
  • a borate-ester present in an amount to deliver 75 ppm to 200 ppm, or 75 ppm to 150 ppm of boron
  • antioxidant 0.1 to 1.2 wt % of antioxidant, wherein at least 20 wt % of the antioxidant may be a phenolic antioxidant,
  • the lubricating composition has a sulfated ash content of 0.4 wt % to 2 wt %, or 0.5 wt % to 1.8 wt %, or 0.5 wt % to not more than 1.5 wt %, and the lubricating composition has a TBN of 6.5 to 15 mg KOH/g (as measured by ASTM D2896-11).
  • the disclosed technology relates to 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 alkaline earth metal sulfonate detergent having a metal ratio of 3 to 9, and a TBN of 81 to 180 mg KOH/g (as measured by ASTM D2896-11),
  • the sulfonate detergents provide a total amount of sulfonate substrate of 0.8 wt % to 3 wt %, or 0.9 wt % to 3 wt %, or 1 wt % to 3 wt % of the lubricating composition,
  • a borated dispersant present in an amount to deliver 125 ppm to 250 ppm of boron, 0.1 to 1.2 wt % of antioxidant, wherein at least 20 wt % of the antioxidant may be a phenolic antioxidant,
  • the lubricating composition has a sulfated ash content of 0.4 wt % to 2 wt %, or 0.5 wt % to 1.8 wt %, or 0.5 wt % to not more than 1.5 wt %, and
  • the lubricating composition has a TBN of 6.5 to 15 mg KOH/g (as measured by ASTM D2896-11).
  • the lubricating composition comprises 0 wt % to 0.2 wt %, or 0 wt % to 0.1 wt % of a phenolic based detergent.
  • the lubricating composition comprises 0.01 wt % to
  • 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 salicylate.
  • the phenolic based detergent may be chosen from a phenate, a salycilate, and a salixarate.
  • the phenate may be a non-sulfur containing phenate, sulfur containing phenate, or a "hybrid" detergent formed with mixed surfactant system, wherein the hybrid is a mixed phenate-salicylate, a sulfonate-phenate, or a sulfonate-phenate-salicylate.
  • the lubricating composition comprises 0 wt % of the phenolic based detergent.
  • the lubricating composition comprises a detergent package of only sulfonate detergents.
  • the sulfonate detergent may be a calcium sulfonate, or magnesium sulfonate. Often the sulfonate may be a calcium sulfonate detergent.
  • the total amount of substrate delivered by the calcium sulfonate detergents may be 1.00 to 1.6 wt %, 1.05 to 1.2 wt %, or 1.05 to 1.1 wt % of the lubricating composition.
  • the 300 TBN or higher alkaline earth metal sulfonate detergent disclosed herein may have a metal ratio of 10 to 40, or 15 to 30, or 20 to 30, or 22 to 25.
  • the calcium sulfonate detergent may have for instance a metal ratio of 10 to 40 has a TBN of 350 to 500, or 375 to 425, and a metal ratio of 20 to 25.
  • the alkaline earth metal sulfonate detergent may have a TBN of 375 to 425, and a metal ratio of 20 to 30, or 22 to 25.
  • the 300 TBN or higher alkaline earth metal sulfonate detergent may be a calcium or magnesium sulfonate detergent, typically a calcium sulfonate detergent.
  • the alkaline earth metal sulfonate detergent having a metal ratio of 3 to 9, and a TBN of 81 to 130 mg KOH/g, or 82 to 100 mg KOH/g.
  • the metal ratio may be metal ratio of 4 to 8, or greater than 5 to 8, and the TBN may be 85 to 95 mg KOH/g.
  • the alkaline earth metal sulfonate detergent may have a metal ratio of 3 to 9, and be a calcium or magnesium sulfonate detergent, typically a calcium sulfonate detergent.
  • the sulfonate detergent having a metal ratio of 3 to 9 and the sulfonate detergent having a metal ratio 10 to 40 are both calcium sulfonate detergents.
  • the compression-ignition internal combustion engine may be referred to as a heavy duty diesel engine.
  • 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 may be set by national government and may be 10,000 kg, or 9,000 kg, or 8,000 kg, or 7,500 kg.
  • the upper ranges of laden mass may be up to 400,000 kg, or up to 200,000 kg, or up to 60,000 kg, or up to 44,000 kg, or up to 40,000 kg.
  • a laden mass above 120,000 may be for an off- highway vehicle.
  • Heavy duty diesel engines are noted to be limited to all motor vehicles with a
  • the internal combustion engine may be a heavy duty diesel compression ignited (or spark assisted compression ignited) internal combustion engine.
  • the lubricating composition is characterized as having (i) a sulfur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulfated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterized as having at least one of (i) a sulfur 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 sulfated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterized as having a sulfated ash content of 0.9 wt % to 1.4 wt %, or 1.05 wt % to 1.2 wt %.
  • the lubricating composition comprises an antioxidant, wherein the phenolic antioxidant comprises at least 40 wt %, or at least 50 wt % of the antioxidant, typically 45 wt % to 90 wt %, or 55 wt % to 80 wt % of the antioxidant.
  • the lubricating composition comprises an aminic antioxidant, typically diarylamine or alkylated diarylamine and include a phenyl-a- naphthylamine (PANA), an alkylated diphenyl amine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • an aminic antioxidant typically diarylamine or alkylated diarylamine and include a phenyl-a- naphthylamine (PANA), an alkylated diphenyl amine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • PANA phenyl-a- naphthylamine
  • the aminic antioxidant comprises at most 60 wt %, or at most 50 wt % of the antioxidant, typically 5 wt % to 55 wt %, or 10 to 45 wt % of the antioxidant.
  • the lubricating composition comprises a sulfurized olefin such as a sulfurized 4-carbobutoxy cyclohexene, or a sulfurized alpha-olefin (such as C10- 24, C14-20, C16-18 alpha-olefins), or sulfurized diisobutylene, or mixtures thereof.
  • a sulfurized olefin antioxidant comprises at most 60 wt %, or at most 50 wt % of the antioxidant, typically 5 wt % to 55 wt %, or 10 to 45 wt % of the antioxidant.
  • the antioxidant comprises a phenolic or an aminic antioxidant or mixtures thereof, and wherein the antioxidant may be present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt %.
  • the lubricating composition disclosed herein may be characterized as having a total base number (TBN) content of 7 to 14, or 7.5 to 12 mg KOH/g, or 8 to 10 mg KOH/g.
  • TBN total base number
  • the disclosed technology 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 disclosed technology 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 and re-refined oils and mixtures thereof.
  • Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
  • 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.
  • Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
  • Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil,), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • animal oils e.g., castor oil,
  • mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerised and interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l-hexenes), poly(l-octenes), poly(l-decenes), and mixtures thereof; alkyl -benzenes (e.g.
  • dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof.
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls
  • diphenyl alkanes alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixture
  • Other synthetic lubricating oils include polyol esters (such as Priolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
  • Synthetic oils may 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 the American
  • the five base oil groups are as follows: Group I (sulfur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulfur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index 80-120); Group III (sulfur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
  • Group I sulfur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120
  • Group II sulfur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index 80-120
  • Group III sulfur content
  • the oil of lubricating viscosity may also be an API Group 11+ base oil, which term refers to a Group II base oil having a viscosity index greater than or equal to 110 and less than 120, as described in SAE publication "Design Practice: Passenger Car Automatic Transmissions", fourth Edition, AE-29, 2012, page 12-9, as well as in US 8,216,448, column 1 line 57.
  • the oil of lubricating viscosity may also be an API Group III+ base oil, which term refers to a Group III+ base oil having a viscosity index greater than or equal to 130.
  • Group III+ are known in the art and is described in "Lube Report", dated February 26, 2014 in an article entitled “SK Sees Group III Shortfall", by Nancy DeMarco. The article may be obtained from http://www.aselube.com/media/11910/sk sees group iii shortfall.pdf.
  • the oil of lubricating viscosity may be an API Group IV oil, or mixtures thereof, i.e., a polyalphaolefin.
  • the polyalphaolefin may be prepared by metallocene catalyzed processes or from a non-metallocene process.
  • the oil of lubricating viscosity comprises an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof.
  • the oil of lubricating viscosity may comprises an API Group I, Group II, Group III, Group IV oil or mixtures thereof.
  • the oil of lubricating viscosity may comprises an API Group I, Group II, Group III oil or mixtures thereof.
  • the oil of lubricating viscosity may comprises an API Group I, Group II oil or mixtures thereof.
  • the oil of lubricating viscosity may comprises an API Group I oil.
  • the oil of lubricating viscosity may comprises an API Group II oil.
  • the amount of the oil of lubricating viscosity present may be typically the balance remaining after subtracting from 100 wt % the sum of the amount of the additive as described herein above, 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 disclosed technology 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 components of the disclosed technology 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.
  • the lubricating composition may be not an aqueous composition.
  • the lubricating composition comprising may have a kinematic viscosity of 2 cSt to 20 cSt (or mm 2 /s) at 100°C, as measured by ASTM D445-14.
  • the lubricating composition may be liquid, i.e., not a gel or semi-solid, at ambient temperatures (5-30°C).
  • the lubricating composition comprises an antioxidant as described herein.
  • the antioxidant comprises a phenolic or an aminic antioxidant or mixtures thereof.
  • the antioxidants include diarylamines, alkylated diarylamines, hindered phenols, or mixtures thereof.
  • the diarylamine or alkylated diarylamine may be a phenyl -a-naphthyl amine (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 antioxidant comprises a mixture of a sulfurized olefin, a phenolic, and aminic antioxidant.
  • the antioxidant mixture may be:
  • phenolic antioxidant comprises at least 40 wt %, or at least 50 wt % of the antioxidant, typically 45 wt % to 90 wt %, or 55 wt % to 80 wt % of the antioxidant;
  • aminic antioxidant comprises at most 60 wt %, or at most 50 wt % of the antioxidant, typically 5 wt % to 55 wt %, or 10 to 45 wt % of the antioxidant;
  • sulfurized olefin antioxidant comprises at most 60 wt %, or at most 50 wt % of the antioxidant, typically 5 wt % to 55 wt %, or 10 to 45 wt % of the antioxidant.
  • the antioxidant mixture may be:
  • phenolic antioxidant comprises at least 40 wt %, or at least 50 wt % of the antioxidant, typically 45 wt % to 90 wt %, or 55 wt % to 80 wt % of the antioxidant;
  • aminic antioxidant comprises at most 60 wt %, or at most 50 wt % of the antioxidant, typically 5 wt % to 55 wt %, or 10 to 45 wt % of the antioxidant;
  • sulfurized olefin antioxidant comprises at most 60 wt %, or at most 50 wt % of the antioxidant, typically 5 wt % to 55 wt %, or 10 to 45 wt % of the antioxidant.
  • the sulfonate detergent of the disclosed technology may be overbased for a detergent having a TBN of at least 300, and neutral to slightly overbased for a TBN of 81 to 130 mg KOH/g as is defined herein.
  • 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 typically comprises at least one calcium sulfonate detergent described herein.
  • the lubricating composition comprises at least one or at least two other sulfonate detergents.
  • the sulfonate detergents of the disclosed technology are known to a person skilled in the art.
  • the lubricating composition further comprises another sulfonate detergent, typically a magnesium, sodium or zinc overbased sulfonate.
  • another sulfonate detergent typically a magnesium, sodium or zinc overbased sulfonate.
  • any additional sulfonate detergent may be a magnesium or sodium sulfonate detergent, with magnesium sulfonate the more typical.
  • the lubricating composition comprises a 300 TBN or higher alkaline earth metal sulfonate detergent having a metal ratio of 10 to 40, and a 82 tovlOO TBN or lower alkaline earth metal sulfonate detergent having a metal ratio of 3 to 9.
  • the lubricating composition comprises a 300 TBN or higher alkaline earth metal sulfonate detergent comprises a magnesium sulfonate detergent having a metal ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal sulfonate detergent comprising a calcium sulfonate detergent having a metal ratio of 1 to 5.
  • the lubricating composition comprises a 300 TBN or higher alkaline earth metal sulfonate detergent comprising a mixture of a calcium sulfonate detergent having a metal ratio of 10 to 40, and a magnesium sulfonate detergent having a metal ratio of 10 to 40, and a 80 TBN or lower alkaline earth metal sulfonate detergent comprises a calcium sulfonate detergent having a metal ratio of 1 to 5.
  • the 300 TBN or higher alkaline earth metal sulfonate detergent and the 80 TBN or lower alkaline earth metal sulfonate detergent may be prepared from the same or different hydrocarbyl-substituted sulfonic acids.
  • the hydrocarbyl-substituted sulfonic acids are alkyl-substituted sulfonic acids.
  • the sulfonate may be prepared from a mono- or di- hydrocarbyl-substituted benzene (or toluene, naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulfonic 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 sulfonic acid may include polypropene benzenesulfonic acid and C 16-C24 alkyl benzenesulfonic acid, or mixtures thereof.
  • the 300 TBN sulfonate detergent may be a predominantly linear alkylbenzene sulfonate 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
  • the predominantly linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
  • the 300 TBN or higher alkaline earth metal sulfonate 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 lubricating composition comprises a calcium sulfonate detergent having a metal ratio of 10 to 40, and a calcium sulfonate detergent having a metal ratio of 3 to 9.
  • the lubricating composition comprises a calcium sulfonate detergent having a metal ratio of 10 to 40, a calcium sulfonate detergent having a metal ratio of 3 to 9, and a magnesium sulfonate detergent having a metal ratio of 12 to 40.
  • the magnesium sulfonate 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 sulfonate may have the same or different hydrocarbyl -substituted sulfonic acids, and are defined the same as described above for calcium sulfonate detergents.
  • the other sulfonate (typically magnesium sulfonate) 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 sulfonate detergents, and optionally a magnesium sulfonate detergent which may be present or absent in different embodiments.
  • the borated compound may be present in an amount to deliver 25 ppm to 300 ppm of boron and the borated compound may be chosen from a borate-ester, a borated dispersant, or mixtures thereof.
  • the boron-containing compound may be borate ester represented by the formula:
  • each R may be independently an organic group and any two adjacent R groups may together form a cyclic group, or
  • boron-containing compound may be borate ester represented by the formula:
  • R, R 1 , R 2 , R 3 and R 4 are independently hydrocarbyl groups of 1 to 12 carbon atoms; and R 5 and R 6 are independently alkylene groups of 1 to 6 carbon atoms, and in one embodiment 2 to 4 carbon atoms, where each R may be independently an organic group and any two adjacent R groups may together form a cyclic group.
  • the boron-containing compound may be a borate ester represented by the formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen or hydrocarbyl groups.
  • each of the hydrocarbyl groups may contain from 1 to 12, or 1 to 4 carbon atoms.
  • the borate ester comprises at least one alkyl group having 10 to about 32 carbon atoms, said alkyl group having a branch at the ⁇ or higher position, said borate ester being present in an amount to provide 1 to 1000 parts per million by weight of boron to the lubricant composition.
  • the borate ester comprises multiple alkyl groups each independently having 10 to 32 carbon atoms, said alkyl groups having a branch at the ⁇ or higher position.
  • the alkyl group may be branched at the ⁇ position.
  • the alkyl group may have a structure represented by -CH2-CH(R 1 )(R 2 ), where R 1 may be an alkyl group of 7 to 18 carbon atoms and R 2 may be an alkyl group having fewer carbon atoms than R 1 .
  • the alkyl group has a structure represented by -CH2-CH(R 1 )(R 2 ), where R 1 may be an alkyl group of 7 to 18 carbon atoms and R 2 may be an alkyl group having two fewer carbon atoms than R 1 .
  • the alkyl group may be derived from a Guerbet alcohol.
  • the alkyl group may be a 2-propylheptyl group, a 2-butyloctyl group, a 2-hexyldecyl group, or a 2-octyldodecyl group.
  • the borate ester may represented by one or more of the formulae:
  • each R may be independently an alkyl group having 10 to 32 carbon atoms and having a branch at the ⁇ or higher position.
  • the borate ester may comprises a trialkylborate.
  • the borate ester may be a material represented by the structure:
  • the borate ester may be present at 75 ppm to 120 ppm, or 80 ppm to 110 ppm of the lubricating composition.
  • the borated compound be may a borated dispersant.
  • the borated dispersant may be a borated succinimide.
  • the borated succinimide may be known to the skilled person and may be prepared by reacting a borating agent such as boric acid, with a polyisobutylene succinimide.
  • a borating agent such as boric acid
  • polyisobutylene succinimide typically has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.
  • the borated 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 borated dispersant may be present at 125 ppm to 250 ppm, or 150 ppm to 200 ppm of the lubricating composition.
  • the lubricating composition may further comprise a non-borated dispersant.
  • the non-borated dispersant may be present at 1 wt % to 8 wt %, or 2.5 wt % to 7 wt %, or 3 wt % to 6 wt % of the lubricating composition.
  • the non-borated dispersant may typically be a succinimide dispersant.
  • the non-borated succinimide dispersant may be derived from polyisobutylene succinimide, wherein the polyisobutylene from which polyisobutylene succinimide may be derived has a number average molecular weight of 350 to 5000, or 750 to 3000 or 1550 to 2500.
  • the non-borated dispersant of both 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 butyl enepolyamine, or mixtures thereof.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be chosen from ethyl enediamine, di ethyl enetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • Non-borated polyisobutylene succinimide dispersants and their preparation are disclosed, for instance in US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743,
  • the non-borated the polyisobutylene succinimide may be present at 2.5 wt % to 6 wt %, or 3 wt % to 5 wt % of the lubricating composition.
  • the non-borated 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 non-borated dispersant may include an amine- functionalized additive may be derived from an amine having at least 3 or 4 aromatic groups.
  • an aromatic group is used in the ordinary sense of the term and is known to be defined by Hiickel theory of 4n+2 ⁇ electrons per ring system. Accordingly, one aromatic group may have 6, or 10, or 14 ⁇ electrons. Hence a benzene ring has 6 ⁇ electrons, a naphthylene ring has 10 ⁇ electrons and an acridine group has 14 ⁇ electrons.
  • An example of the amine having at least 3 or 4 aromatic groups may be represented by Formula (1):
  • R 1 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
  • R 2 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
  • U may be an aliphatic, alicyclic or aromatic group, with the proviso that when U may be aliphatic, the aliphatic group may be linear or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms;
  • w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).
  • R 1 may be hydrogen or a C1-5 alkyl group (typically hydrogen
  • R 2 may be hydrogen or a C1-5 alkyl group (typically hydrogen U may be an aliphatic, alicyclic or aromatic group, with the proviso that when U may be aliphatic, the aliphatic group may be linear or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and
  • w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).
  • the compound of Formula (la) may also be represented by:
  • each variable U, R 1 , and R 2 are the same as described above and w may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).
  • Examples of an amine having at least 3 or 4 aromatic groups may be represented by any of the following Formulae (2) and/or (3):
  • the amine having at least 3 or 4 aromatic groups may include mixtures of compounds represented by the formulae disclosed above.
  • compounds of Formulae (2) and (3) may also react with the aldehyde described below to form acridine derivatives.
  • Acridine derivatives that may be formed include compounds illustrated represented by Formula (2a) or (3a) to (3c) below.
  • a person skilled in the art will also appreciate that other acridine structures may be possible where the aldehyde reacts with other with benzyl groups bridged with the > H group. Examples of acridine structures include those represented by Formulae (2a), (3a) or (3b) or (3c):
  • N-bridged aromatic rings are capable of such further condensation and perhaps aromaticisation.
  • One other of many possible structures include Formula (3b):
  • Examples of the amine having at least 3 or 4 aromatic groups may be bis[p-(p- aminoanilino)phenyl]-methane, 2-(7-amino-acridin-2-ylmethyl)-N-4- ⁇ 4-[4-(4-amino- phenylamino)-benzyl]-phenyl ⁇ -benzene- 1,4-diamine, N-4- ⁇ 4-[4-(4-amino- phenylamino)-benzyl]-phenyl ⁇ -2-[4-(4-amino-phenylamino)-cyclohexa-l,5- di enylmethyl] -benzene- 1,4-diamine, N-[4-(7-amino-acridin-2-ylmethyl)-phenyl]- benzene-l,4-diamine, or mixtures thereof.
  • the amine having at least 3 or 4 aromatic groups may be bis[p-(p-aminoanilino)phenyl]-methane, 2-(7-amino-acridin-2-ylmethyl)-N-4- ⁇ 4-[4-(4- amino-phenylamino)-benzyl]-phenyl ⁇ -benzene-l,4-diamine or mixtures thereof.
  • the amine having at least 3 or 4 aromatic groups may be prepared by a process comprising reacting an aldehyde with an amine (typically 4 aminodiphenylamine).
  • the resultant amine may be described as an alkylene coupled amine having at least 3 or 4 aromatic groups, at least one - H 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.
  • the amine having at least 3 or 4 aromatic groups may also be prepared by the methodology described in Berichte der Deutschen Chemischenmaschine (1910), 43, 728-39.
  • the amine having at least 3 or 4 aromatic groups may be obtained/obtainable by a process comprising reacting isatoic anhydride or alkyl substituted isatoic anhydride, with an aromatic amine with at least two aromatic groups and a reactive primary or secondary amino group.
  • the resultant material may be described as an anthranilic derivative.
  • the anthranilic derivative may be prepared in a reaction containing isatoic anhydride or alkyl substituted isatoic anhydride and an aromatic amine selected from the group consisting of xylylenediamine, 4-aminodiphenylamine, 1,4- dimethylphenylenediamine, and mixtures thereof.
  • the aromatic amine may be 4-aminodiphenylamine.
  • the process described above to prepare the anthranilic derivative may be carried out at a reaction temperature in the range of 20 ° C to 180 ° C, or 40 ° C to 110 ° C.
  • the process may or may not be carried out in the presence of a solvent.
  • a suitable solvent include water, diluent oil, benzene, t-butyl benzene, toluene, xylene, chlorobenzene, hexane, tetrahydrofuran, or mixtures thereof.
  • the reactions may be performed in either air or an inert atmosphere. Examples of suitable inert atmosphere include nitrogen or argon, typically nitrogen.
  • the amine-functionalized additive may be the reaction product of the amine having at least 3 or 4 aromatic groups with a carboxylic functionalized polymer.
  • the resultant product obtained may be described as being an amine-functionalized carboxylic functionalized polymer.
  • the carboxylic functionalized polymer backbone may be a homopolymer or a copolymer, provided that it contains at least one carboxylic acid functionality or a reactive equivalent of carboxylic acid functionality (e.g., anhydride or ester).
  • the carboxylic functionalized polymer may have a carboxylic acid functionality (or a reactive equivalent of carboxylic acid functionality) grafted onto the backbone, within the polymer backbone or as a terminal group on the polymer backbone.
  • the carboxylic functionalized polymer may be a polyisobutylene-succinic anhydride, a maleic anhydride-styrene copolymer, an ester of a maleic anhydride-styrene copolymer, an alpha olefin-maleic anhydride copolymer, or a maleic anhydride graft copolymer of (i) a styrene-ethylene-alpha olefin polymer, (ii) a hydrogenated alkenyl aryl conjugated diene copolymer ((that is, a hydrogenated alkenyl arene conjugated diene copolymer, in particular a hydrogenated copolymer of styrene-butadiene), (iii) a polyolefin grafted with maleic anhydride (in particular ethylene-propylene copolymer), or (iv) a isoprene polymer (in particular
  • the carboxylic functionalized polymer described herein is known in lubricant technology.
  • lubricant technology for example:
  • esters of maleic anhydride and styrene-containing polymers are known from US Patent 6,544,935;
  • copolymers derived from isobutylene and isoprene have been used in preparing dispersants and are reported in International publication WO 01/98387;
  • grafted styrene-butadiene and styrene-isoprene copolymers are described in a number of references including DE 3,106,959; and US Patents 5,512, 192, and 5,429,758;
  • esters of (alpha-olefin maleic anhydride) copolymers have been described in US Patent 5,670,462;
  • copolymers of isobutylene and conjugated dienes have been described in US Patents 7,067,594 and 7,067,594 and US Patent Application US 2007/0293409; and terpolymers of ethylene, propylene and non- conjugated diene (such as dicyclopentadiene or butadiene) and described in US Patents 5,798,420 and 5,538,651.
  • polymers mentioned in (iii), (iv) and (viii) that contain dienes e.g., butadiene or isoprene) are partially or wholly hydrogenated.
  • the polymer backbone (other than a polyisobutylene) of the disclosed technology may have a number average molecular weight (by gel permeation chromatography, polystyrene standard), which may be up to 150,000 or higher, e.g., 1,000 or 5,000 to 150,000 or to 120,000 or to 100,000.
  • An example of a suitable number average molecular weight range includes 10,000 to 50,000, or 6,000 to 15,000, or 30,000 to 50,000.
  • the polymer backbone has a number average molecular weight of greater than 5,000, for instance, greater than 5000 to 150,000. Other combinations of the above-identified molecular weight limitations are also contemplated.
  • the polymer backbone is a polyisobutylene
  • its number average molecular weight (by gel permeation chromatography, polystyrene standard), may be 350 to 5000, or 550 to 3000 or 750 to 2500.
  • a polyisobutylene succinic anhydride may be derived from a polyisobutylene with any of the foregoing molecular weights.
  • Commercially available polyisobutylene polymers have a number average molecular weight of 550, 750, 950-1000, 1550, 2000, or 2250. Some of the commercially available polyisobutylene polymers may obtain the number average molecular weights shown above by blending one or more polyisobutylene polymers of different weights.
  • the product may be obtained/obtainable by reacting a carboxylic functionalized polymer with an amine-functionalized additive having at least 3 or 4 aromatic groups, at least one - H 2 functional group, and at least 2 secondary or tertiary amino groups.
  • the amine-functionalized additive having at least 3 or 4 aromatic groups may be reacted with the carboxylic functionalized polymer under known reaction conditions.
  • the reaction conditions are known to a person skilled in the art for forming imides and/or amides of carboxylic functionalized polymers.
  • the amine-functionalized carboxylic functionalized polymer obtained/obtainable by reacting a carboxylic functionalized polymer with an amine having at least 3 or 4 aromatic groups, at least one - H 2 functional group, and at least 2 secondary or tertiary amino groups may in certain embodiment be represented by the Formulae (4) and/or (5):
  • BB may be a polymer backbone and may be polyisobutylene, or copolymers of (i) hydrogenated alkenyl aryl conjugated diene copolymers (in particular hydrogenated copolymers of styrene-butadiene), (ii) polyolefins (in particular ethylene-alphaolefins such as ethylene-propylene copolymers), (iii) hydrogenated isoprene polymers (in particular hydrogenated styrene-isoprene polymers), or (iv) a copolymer of isoprene and isobutylene.
  • hydrogenated alkenyl aryl conjugated diene copolymers in particular hydrogenated copolymers of styrene-butadiene
  • polyolefins in particular ethylene-alphaolefins such as ethylene-propylene copolymers
  • hydrogenated isoprene polymers in particular hydrogenated sty
  • BB may be substituted with one succinimide group as is shown in formulae (4) and (5), or it may be substituted by multiple succinimide groups.
  • BB may be a copolymer of isoprene and isobutylene.
  • additional structures may also be formed including trimers, tetramers, higher-mers or mixtures thereof.
  • trimers tetramers, higher-mers or mixtures thereof.
  • Formulae (4) and (5) may also be replaced, in whole, or in part, by the amine of formulae (2a), (3), (3 a), or mixtures thereof.
  • BB may be polyisobutylene
  • the resultant carboxylic functionalized polymer may typically be polyisobutylene succinic anhydride.
  • w as defined in Formula (1) may be 1 to 5, or 1 to 3.
  • BB may be other than polyisobutylene, and has maleic anhydride (or other carboxylic acid functionality) grafted thereon
  • one or more of the grafted maleic anhydride groups may be a succinimide of the amine upon reaction with the amine.
  • the number of succinimide groups may be 1 to 40, or 2 to 40, or 3 to 20.
  • the amine-functionalized carboxylic functionalized polymer may be obtained/obtainable by reacting a carboxylic functionalized polymer derived from maleic anhydride-styrene copolymers, esters of maleic anhydride-styrene copolymers, alpha- olefin maleic anhydride copolymers; or mixtures thereof with an amine having at least 3 or 4 aromatic groups, at least one - ⁇ 2 functional group, and at least 2 secondary or tertiary amino groups.
  • the product of this type may be described as an alternating copolymer.
  • one or more of the maleic anhydride derived groups may have a group represented by Formula (6):
  • R 1 , R 2 and U are described previously, and the group of Formula (6) may be bonded to components of the polymer backbone through one or both wavy bonds as shown on the maleic ring structure above.
  • the second wavy bond may be to a hydrogen.
  • the amine containing group in formula (6) may also be replaced by the amine in formula (3), or mixtures thereof.
  • the amine-functionalized carboxylic functionalized polymer may be derived from a polyisobutylene polymer backbone (represented by PIB in formula 7 below). A more detailed description of the polyisobutylene polymer backbone is described previously in the description.
  • An example of suitable structures of the anthranilic derivative derived from polyisobutylene, the anthranilic derivative and 4-aminodiphenylamine may be represented by Formula (7):
  • the amine-functionalized carboxylic functionalized polymer may be derived from one of the aromatic amines and from a non-polyisobutylene polymer backbone.
  • Examples of suitable structures of the anthranilic derivative derived from 4-aminodiphenylamine may be represented by Formula (8):
  • BB may be a polymer (typically BB may be an ethylene-propylene copolymer derived from ethylene-propylene copolymers). As shown BB is grafted with maleic anhydride and functionalized to form the imide group, and u may be the number of grafted units within [ ], typically u may be in the range of 1 to 2000, or 1 to 500, or 1 to 250, or 1 to 50, 1 to 20, 1 to 10, or 1 to 4.
  • the amine-functionalized additive may be based upon a polyisobutylene defined by BB in formula (4) or formula (5) above.
  • the non-borated dispersant comprises an amine having at least 3 or 4 aromatic groups may be represented by Formula (1) reacted with polyisobutylene anhydride.
  • the non-borated dispersant may be present at 0.25 wt % to 8 wt %, or 0.5 wt % to 5 wt %, 1 wt % to 4.5 wt % or 1.6 wt % to 2.5 wt % of the lubricating composition.
  • Dispersant Viscosity Modifier 0.5 wt % to 5 wt %, 1 wt % to 4.5 wt % or 1.6 wt % to 2.5 wt % of the lubricating composition.
  • the lubricating composition of the disclosed technology in one embodiment further contains a dispersant viscosity modifier.
  • the dispersant viscosity modifier may be present at 0.01 wt % to 3 wt %, or 0.05 wt % to 1.5 wt %, or 0.1 wt % to 1 wt %, or 0.1 to 0.5 wt %.
  • the lubricating composition disclosed herein further comprises a dispersant viscosity modifier.
  • the dispersant viscosity modifier may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalized 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]).
  • an acylating agent such as maleic anhydr
  • the dispersant viscosity modifier comprises an olefin copolymer further functionalized with a dispersant amine group.
  • the olefin copolymer may be an ethylene-propylene copolymer.
  • the olefin copolymer has a number average molecular weight of 5000 to
  • 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 C3-10 a-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 H 2 -Ar or T-NH-Ar, where T may be alkyl or aromatic, Ar may be an aromatic group, including nitrogen-containing or amino- substituted aromatic groups and Ar groups including any of the following structures
  • 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-alkyl anilines such as N-methylaniline and N-butylaniline, di-(para-methylphenyl)amine, 4-aminodiphenylamine, ⁇ , ⁇ -dimethylphenylenediamine, naphthyl amine, 4-(4- nitrophenylazo)aniline (disperse orange 3), sulphamethazine, 4-phenoxyaniline, 3-nitro- aniline, 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-alkyl anilines 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, aminoperimidines, mercaptotriazoles, aminophenothiazines, aminopyridines, aminopyrazines, aminopyrimidines, pyridines, pyrazines, pyrimidines, aminothiadiazoles, 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:
  • R vm and R lx are independently alkyl or alkoxy groups such as methyl, methoxy, or ethoxy.
  • R vm and R lx are both -OCH3 and the material is known as Fast Blue RR [CAS# 6268-05-9].
  • R lx may be -OCH3 and R vm may be -CH3, and the material is known as Fast Violet B [99-21-8]. When both R vm and R lx 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 Al, may also be used for the purposes of the disclosed technology. 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 - H2 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.
  • an aliphatic aldehyde examples 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 Chemischenmaschine (1910), 43, 728-39.
  • R 1 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
  • R 2 may be hydrogen or a C1-5 alkyl group (typically hydrogen);
  • U may be an aliphatic, alicyclic or aromatic group, with the proviso that when U may be aliphatic, the aliphatic group may be linear or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms;
  • w may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).
  • the aromatic amine includes 4-aminodiphenylamine, aldehyde (typically formaldehyde) coupled 4-aminodiphenylamine, nitro-aniline (3- nitro- aniline), disperse orange-3 (D03), 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).
  • Other Performance Additives as described herein below.
  • the lubricating composition of the disclosed technology 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, 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 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
  • Friction modifiers may also encompass materials such as sulfurized 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, sulfurized 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 thio- carbamates, and bis(S-alkyldithiocarbamyl) disulfides.
  • 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 may be at least 8.
  • the antiwear agent may in one embodiment include a citrate as is disclosed in US Patent
  • Another class of additives includes 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 may be a titanium (IV) alkoxide.
  • the titanium alkoxide may be 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 may be titanium (IV) isopropoxide.
  • the titanium alkoxide may be 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 may be oleic acid.
  • the oil soluble titanium compound may be a titanium carboxylate.
  • the titanium (IV) carboxylate may be 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.
  • the lubricating composition may further include a phosphorus-containing antiwear agent based upon zinc dialkyldithiophosphate, or mixtures thereof.
  • the amount of zinc dialkyldithiophosphate present may deliver 100 ppm to 1000 ppm, or 200 ppm to 900 ppm, or 350 ppm to 900 ppm of phosphorus.
  • the zinc dialkyldithiophosphate may be derived from aliphatic or aromatic hydrocarbyl alcohols; the hydrocarbyl; alcohols may be primary or secondary alcohols.
  • a zinc dialkyldithiophosphate (or ZDDP) derived from secondary alcohols is said to be a secondary ZDDP.
  • a ZDDP derived from primary alcohols is said to be a primary ZDDP.
  • ZDDP prepared from a mixture of primary and secondary alcohols is said to be a mixed primary/secondary ZDDP.
  • the ZDDP may be represented by the following structure: wherein each R may be independently a primary or secondary hydrocarbyl group containing from 1 to 24, for example from 2 to 12, carbon atoms and including groups such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic hydrocarbyl groups. In an embodiment, R may be alkyl groups of 2 to 8 carbon atoms.
  • R may be, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, and butenyl.
  • the R group of the zinc dithiophosphate may be derived, for example, from a primary alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, octadecanol, propenol, butenol, 2-ethylhexanol: a secondary alcohol such as isopropyl alcohol, secondary butyl alcohol, isobutanol, 3-methylbutan-2-ol, 2-pentanol, 4-methyl-2-pentanol, 2-hexanol, 3-hexanol, amyl alcohol, an aryl alcohol such as phenol, substituted phenol (particularly alkylphenol such as butylphenol, octylphenol, nonylphenol, dodecylphenol), disubstituted phenol.
  • a primary alcohol such as
  • Certain primary diols may also be used to prepare ZDDP; suitable primary diols include ethylene glycol, propylene gycol, and esters of polyhydric alcohol such as glycerol monooleate and combinations thereof.
  • ZDDP may be prepared from a combination of primary alcohols and primary diols.
  • the R group of the ZDDP may be independently a primary alkyl, a secondary alkyl, an aryl group, or mixtures thereof.
  • the R group of the ZDDP may be a secondary alkyl group.
  • Extreme Pressure (EP) agents include compounds that are soluble in the oil include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS 2 derivatives of dispersants (typically succinimide dispersants), derivative of chlorinated hydrocarbon EP agents and phosphorus EP agents.
  • EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl- substituted 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof, organic sulfides and polysulfides such as dibenzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite,
  • Foam inhibitors that may be useful in the compositions of the disclosed technology 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
  • pour point depressants that may be useful in the compositions of the disclosed technology 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 sulpholene 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 characterized as having (i) a sulfur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulfated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterized as having at least one of (i) a sulfur 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 sulfated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterized as having a sulfated ash content of 0.5 wt % to 1.2 wt %.
  • the lubricating composition may have a total sulfated ash content of 1.2 wt % or less.
  • the sulfur 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 sulfur 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 sulfated 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 sulfated ash content may be 0.5 wt % to 1.1 wt % of the lubricating composition.
  • the lubricating composition may be characterized as having (i) a sulfur content of 0.5 wt % or less, (ii) a phosphorus content of 0.15 wt % or less, and (iii) a sulfated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterized as having at least one of (i) a sulfur 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 sulfated ash content of 0.5 wt % to 1.5 wt % or less.
  • the lubricating composition may be characterized as having a sulfated ash content of 0.5 wt % to 1.2 wt %.
  • 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 16, 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 15W-40 engine lubricants in Group II base oil of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, as well as other performance additives as follows (Table 1).
  • the phosphorus, sulfur and ash contents of each of the examples are also presented in the table in part to show that each example has a similar amount of these materials and so provide a proper comparison between the comparative and invention examples.
  • lubricants include low levels of corrosion inhibitors, foam inhibitor, and pourpoint depressant [0214]
  • the lubricants are evaluated for deposit control, copper and lead corrosion, and friction and wear in a series of bench tests and fired engine tests.
  • Deposit control is evaluated using industry standard tests TEOST 33C (ASTM D6335), MHT TEOST (ASTM D7097B), the Caterpillar IK (ASTM D6750) single cylinder engine test, and the Mack T-12 engine test.
  • Corrosion is evaluated using an extended version of the high temperature corrosion bench test (HTCBT as described in ASTM D6594.
  • the lubricating composition may have at least one of deposit control, wear control and/or Cu/Pb corrosion control.
  • 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.
EP16710605.3A 2015-03-09 2016-03-07 Method of lubricating an internal combustion engine Withdrawn EP3268456A1 (en)

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US20220145204A1 (en) 2022-05-12
CN107636133A (zh) 2018-01-26

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