WO2015106083A1 - Procédé de lubrification d'un moteur à combustion interne - Google Patents

Procédé de lubrification d'un moteur à combustion interne Download PDF

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Publication number
WO2015106083A1
WO2015106083A1 PCT/US2015/010793 US2015010793W WO2015106083A1 WO 2015106083 A1 WO2015106083 A1 WO 2015106083A1 US 2015010793 W US2015010793 W US 2015010793W WO 2015106083 A1 WO2015106083 A1 WO 2015106083A1
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WO
WIPO (PCT)
Prior art keywords
sulphonate detergent
detergent
tbn
alkaline earth
dispersant
Prior art date
Application number
PCT/US2015/010793
Other languages
English (en)
Inventor
Mary Galic Raguz
John G. Loop
Original Assignee
The Lubrizol Corporation
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 The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to CA2936276A priority Critical patent/CA2936276A1/fr
Priority to CN201580012444.XA priority patent/CN106103674A/zh
Priority to EP15701084.4A priority patent/EP3092289B1/fr
Priority to SG11201605533RA priority patent/SG11201605533RA/en
Priority to US15/110,106 priority patent/US20160326452A1/en
Priority to ES15701084T priority patent/ES2819503T3/es
Publication of WO2015106083A1 publication Critical patent/WO2015106083A1/fr
Priority to US16/720,552 priority patent/US20200140777A1/en
Priority to US17/511,928 priority patent/US20220049178A1/en

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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
    • 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
    • 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
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    • 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
    • C10M2215/086—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
    • C10M2219/04—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
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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
    • 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
    • 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
    • C10M2219/08—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
    • 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
    • C10M2219/08—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
    • 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
    • C10M2219/08—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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C10N2030/06—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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

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, 1.5 wt % to 10 wt % of an ashless dispersant, 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, wherein the lubricating composition comprises 0 wt % to 0.2 wt % of a phenolic based detergent, the ratio of higher alkaline earth metal sulphonate detergent to lower alkaline earth metal sulphonate detergent is 80:20 to 20:80, the total amount of soap delivered by the calcium sulphonate detergents is 0.4 wt % to 1.5 wt % of the lubricating composition, and the lubricating
  • 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 C 12 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 C 14 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 201 1/0124539 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.
  • 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 invention 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:
  • the lubricating composition comprises 0 wt % to 0.2 wt % of a phenolic based detergent
  • the ratio of higher alkaline earth metal sulphonate detergent to lower alkaline earth metal sulphonate detergent is 80:20 to 20:80
  • the total amount of soap delivered by the calcium sulphonate detergents is 0.4 wt % to 1.5 wt % (or 0.4 to 1 wt %, or 0.5 to 1 wt %) of the lubricating composition, and
  • the lubricating composition has a sulphated ash content of not more than 1.5 wt %.
  • the ratio of higher alkaline earth metal sulphonate detergent to lower alkaline earth metal sulphonate detergent is 70:30 to 30:70, or 65 :35 to 35 :65.
  • the total amount of soap delivered by the sulphonate detergent is 0.4 wt % to 1 wt %, or 0.5 to 0.8 wt % of the lubricating composition.
  • the lubricating composition comprises 0 wt % to 0.1 wt % of a phenolic based detergent.
  • 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 selected from of a phenate, and a salycilate.
  • the phenolic based detergent may be selected from of a phenate, a salycilate, and a salixarate.
  • the phenate may be a non-sulphur containing phenate, sulphur containing phenate, or a "hybrid" detergents 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 lubricating composition comprises 0.01 wt % to 0.2 wt %, or 0.05 wt % to 0.1 wt % of the phenolic based detergent.
  • 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 diesel engines
  • the European Union indicates that for new light duty vehicles (passenger cars and light commercial vehicles) included within the scope of ACEA testing section "C" have a "technically permissible maximum laden mass” not exceeding 2610 kg.
  • 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 hydro cracking, hydro gen ation, and hydro finishing, unrefined, refined, re-refined oils or mixtures thereof.
  • oil derived from hydro cracking, hydro gen ation, and hydro finishing unrefined, refined, re-refined oils or mixtures thereof.
  • 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 1 1 , 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 two sulphonate detergents.
  • the sulphonate detergents of the invention are known to a person skilled in the art.
  • Both the lower and higher TBN sulphonate detergent defined by the present invention are alkaline earth metal sulphonate detergents.
  • the alkaline earth metal is chosen from calcium, magnesium, or barium.
  • calcium, or magnesium is typically chosen from calcium, or magnesium.
  • the 300 TBN or higher calcium sulphonate detergent and the 80 TBN or lower calcium 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
  • 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-C24 alkyl benzenesulphonic acid
  • 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 calcium 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
  • 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 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 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 contains an ashless dispersant.
  • the ashless dispersant comprises a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or mixtures thereof.
  • the dispersant may be present as a single dispersant.
  • the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.
  • the ashless dispersant comprises a succinimide dispersant.
  • the succinimide dispersant 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.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be selected from of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene- pentamine, pentaethylenehexamme, polyamine still bottoms, and mixtures thereof.
  • the ashless dispersant may be a polyolefin succinic acid ester, amide, or ester-amide.
  • a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof.
  • a polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and a polyamine as described above.
  • the ashless dispersant may be an N-substituted long chain alkenyl succinimide.
  • An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide.
  • the polyisobutylene from which polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.
  • 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,
  • the dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents such as boric acid
  • boron compounds such as boric acid
  • urea such as urea
  • thiourea dimercaptothiadiazoles
  • carbon disulphide aldehydes
  • ketones carboxylic acids such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as tere
  • the ashless dispersant may have a TBN on an oil free basis of 20 or more, 40 or more, 70 or more, or 85 or more, such as 50 to 130, or 80 to 120, or
  • the ashless dispersant may be present at 2.5 wt % to 6 wt %, or 3 wt % to 5 wt %.
  • the ahsless dispersant may comprise a succinimide dispersant, wherein the succinimide dispersant is present at. 2.5 wt % to 6 wt %, or 3 wt % to 5 wt %.
  • the 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.
  • 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.
  • the ashless dispersant may typically comprise a dispersant package of two or more dispersants.
  • the dispersant package may comprise: 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 1 150, and
  • a polyisobutylene succinimide 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 350 to 5000, or 750 to 3000 or 1550 to 2500.
  • the polyisobutylene succinimide derived from a polyisobutylene having a number average molecular weight of 1550 to 2500 may be present at
  • the ashless dispersant further comprises a polyisobutylene succinimide derived from a polyisobutylene having a number average molecular weight of 1550 to 2500 and may be present at 0.1 to 2 wt %, or 0.2 wt % to 1 wt %.
  • 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
  • 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 olefmic carboxylic acid acylating agent onto a polymer of 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of C3_io ⁇ -monoolefm, 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 dispersant viscosity modifier may be a reaction product of: (a) a polymer comprising carboxylic acid functionality or a reactive equivalent thereof, said polymer having a number average molecular weight of greater than 5,000; and (b) an amine component comprising at least one aromatic amine containing at least one amino group capable of condensing with said carboxylic acid functionality to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom, wherein said aromatic amine is selected from of (i) a nitro-substituted aniline,
  • 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:
  • 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 include aniline, N-alkylanilines such as N-methyl aniline 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-methyl aniline and N- butylaniline
  • di-(para-methylphenyl)amine 4-
  • 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, amino- pyrazines, aminopyrimi dines, 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:
  • R vm and R 1X are independently alkyl or alkoxy groups such as methyl, methoxy, or ethoxy.
  • R vm and R 1X 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] .
  • 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 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 hybridized within an aromatic ring.
  • the aromatic amine may also comprise an amine formed by reacting an aldehyde with 4 -amino dip henyl amine.
  • 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.
  • 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 Ci_ 5 alkyl group (typically hydrogen);
  • R may be hydrogen or a Ci_ 5 alkyl group (typically hydrogen);
  • U may be an aliphatic, alicyclic or aromatic group, with the proviso that when U is 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).
  • 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-a- 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-butyl- phenol.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba.
  • the friction modifier may be selected from of 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 alcohol
  • 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 thio- carbamates, and bis(S-alkyldithiocarbamyl) disulphides.
  • the antiwear agent may in one embodiment include a tartrate, or tartrimide as disclosed in International Publication WO 2006/04441 1 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
  • 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 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 that are soluble in the oil include sulphur- and chlorosulphur-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; sulphurised olefins (such as sulphurised isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-l ,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 trihydro carbon 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
  • 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
  • the phosphorus content may be 0.04 wt % to 0.12 wt %. In one embodiment 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.
  • 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).
  • OCP ethylene-propylene copolymer (having a number average molecular weight of about 8000) based DVM booster aminated with aromatic amine
  • 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.
  • RFWT Roller Follower Wear Test
  • CAT IN Caterpillar IN
  • Table 2 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.
  • 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.

Abstract

L'invention concerne un procédé de lubrification d'un moteur à combustion interne et à allumage par compression présentant une masse maximale en charge supérieure à 2 700 kg. Ledit procédé comprend les étapes consistant à amener jusqu'au moteur une composition lubrifiante contenant une huile lubrifiante, 1,5 à 10 % en poids d'un agent dispersant sans cendres, un détergent à base d'un sulfonate de métal alcalino-terreux présentant un indice de base supérieur ou égal à 300 et une proportion relative de métaux variant de 10 à 40, et un détergent à base d'un sulfonate de métal alcalino-terreux présentant un indice de base inférieur ou égal à 80 et une proportion relative de métaux variant de 1 à 5, ladite composition lubrifiante contenant de 0 à 0,2 % en poids d'un détergent phénolique, le rapport entre le premier détergent à base d'un sulfonate de métal alcalino-terreux et le second détergent à base d'un sulfonate de métal alcalino-terreux variant de 80/20 à 20/80, la quantité totale de savon provenant des détergents à base d'un sulfonate de calcium variant de 0,4 à 1,5 % en poids de la composition lubrifiante et la composition lubrifiante présentant une teneur en cendres sulfatées ne dépassant pas 1,5 % en poids.
PCT/US2015/010793 2014-01-10 2015-01-09 Procédé de lubrification d'un moteur à combustion interne WO2015106083A1 (fr)

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CA2936276A CA2936276A1 (fr) 2014-01-10 2015-01-09 Procede de lubrification d'un moteur a combustion interne
CN201580012444.XA CN106103674A (zh) 2014-01-10 2015-01-09 润滑内燃机的方法
EP15701084.4A EP3092289B1 (fr) 2014-01-10 2015-01-09 Méthode à lubrifier un moteur à combustion
SG11201605533RA SG11201605533RA (en) 2014-01-10 2015-01-09 Method of lubricating an internal combustion engine
US15/110,106 US20160326452A1 (en) 2014-01-10 2015-01-09 Method of lubricating an internal combustion engine
ES15701084T ES2819503T3 (es) 2014-01-10 2015-01-09 Método de lubricación de un motor de combustión interna
US16/720,552 US20200140777A1 (en) 2014-01-10 2019-12-19 Method Of Lubricating An Internal Combustion Engine
US17/511,928 US20220049178A1 (en) 2014-01-10 2021-10-27 Method Of Lubricating An Internal Combustion Engine

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US201461925678P 2014-01-10 2014-01-10
US61/925,678 2014-01-10

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US15/110,106 A-371-Of-International US20160326452A1 (en) 2014-01-10 2015-01-09 Method of lubricating an internal combustion engine
US15/110,135 Continuation US20160326453A1 (en) 2014-01-10 2015-01-09 Method of lubricating an internal combustion engine

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WO2019018326A1 (fr) 2017-07-17 2019-01-24 The Lubrizol Corporation Composition de lubrifiant à faible teneur en zinc
CN109790481A (zh) * 2016-09-14 2019-05-21 路博润公司 润滑组合物和润滑内燃机的方法

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CN110770331B (zh) * 2017-06-30 2023-01-24 雪佛龙奥伦耐有限责任公司 含有异构化酚基清净剂的低粘度发动机油
US20190127658A1 (en) 2017-10-30 2019-05-02 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
CN107987922A (zh) * 2017-12-08 2018-05-04 锦州新兴石油添加剂有限责任公司 一种高性能cj-4重负荷柴机油复合剂及其制备方法和应用
US20190264128A1 (en) * 2018-02-28 2019-08-29 Chevron Oronite Company Llc Functional fluids lubricating oil compositions
CN114774184B (zh) * 2022-04-13 2023-03-17 新乡市瑞丰新材料股份有限公司 一种含高碱值硼酸盐的燃气发动机油复合剂及其制备方法

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SG11201605533RA (en) 2016-08-30
ES2819503T3 (es) 2021-04-16
CN106103674A (zh) 2016-11-09
US20160326452A1 (en) 2016-11-10
EP3092289B1 (fr) 2020-08-12
CA2936276A1 (fr) 2015-07-16

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