EP3116980B1 - 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
EP3116980B1
EP3116980B1 EP15710331.8A EP15710331A EP3116980B1 EP 3116980 B1 EP3116980 B1 EP 3116980B1 EP 15710331 A EP15710331 A EP 15710331A EP 3116980 B1 EP3116980 B1 EP 3116980B1
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EP
European Patent Office
Prior art keywords
soot
lubricating
group
lubricating composition
dispersant
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EP15710331.8A
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German (de)
English (en)
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EP3116980A1 (fr
Inventor
Mary Galic Raguz
John G. Loop
My Hang T. TRUONG
William O'RYAN
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Lubrizol Corp
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2215/28—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
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/019—Shear stability
    • 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
    • C10N2030/10—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
    • C10N2030/52—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
    • C10N2040/255—Gasoline engines

Definitions

  • the invention provides a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt % soot resulting from operation of the engine, and wherein the lubricant composition comprises an oil of lubricating viscosity, and 0.2 wt % to 3 wt % of a soot dispersing additive, wherein the soot dispersing additive comprises a polymer chain having a number average molecular weight of 500 to 20,000, and a shear stability index of 0 to 20 and is a dispersant comprising an aromatic amine moiety obtained by reacting a polyisobutylene succinic anhydride with an amine having at least 4 aromatic groups and an aldehyde, wherein the aromatic amine has the formula defined in claim 1.
  • the present invention allows for an internal combustion engine (typically a compression ignition engine) to have at least one of reduced oil mist separator filter plugging, and reduced deposits such as slimy/sludgy to hard-tacky deposits.
  • an internal combustion engine typically a compression ignition engine
  • reduced oil mist separator filter plugging and reduced deposits such as slimy/sludgy to hard-tacky deposits.
  • 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 and novel characteristics of the composition or method under consideration.
  • compression ignition 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 ignition internal combustion engine, as well as spark assisted compression ignition internal combustion engines.
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt %, or 0.3 wt % to 6 wt % (or typically 0.5 wt % to 4 wt %) soot resulting from operation of the engine, and wherein the lubricant composition comprises an oil of lubricating viscosity, and 0.2 wt % to 3 wt % of a soot dispersing additive, wherein the soot dispersing additive comprises a polymer chain having a number average molecular weight of 500 to 20,000, and a shear stability index of 0 to 20 and is a dispersant comprising an aromatic amine moiety obtained by reacting a polyisobutylene succinic anhydride with an amine having at least 4 aromatic groups and an aldehyde, wherein the aromatic amine has the formula defined in claim 1.
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt % soot resulting from operation of the engine, and wherein the lubricant composition comprises an oil of lubricating viscosity, and 0.2 wt % to 3 wt % of a soot dispersing additive, wherein the soot dispersing additive comprises a polymer chain having a number average molecular weight of 500 to 20,000 and a shear stability index of 0 to 20, and the soot dispersing additive is a dispersant comprising an aromatic amine moiety obtained/obtainable by reacting a polyisobutylene succinic anhydride with an amine having at least 4 aromatic groups and an aldehyde (such as formaldehyde).
  • the aromatic amine is represented by formula: wherein each variable
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt % soot resulting from operation of the engine, and wherein the lubricant composition comprises an oil of lubricating viscosity, and 0.2 wt % to 3 wt % of the soot dispersing additive.
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt %, or 0.3 wt % to 6 wt % (or typically 0.5 wt % to 4 wt %) soot resulting from operation of the engine, and wherein the lubricant composition comprises:
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt %, or 0.3 wt % to 6 wt % (or typically 0.5 wt % to 4 wt %) soot resulting from operation of the engine, and wherein the lubricant composition comprises:
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt %, or 0.3 wt % to 6 wt % (or typically 0.5 wt % to 4 wt %) soot resulting from operation of the engine, and wherein the lubricant composition comprises:
  • the invention relates to a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt %, or 0.3 wt % to 6 wt % (or typically 0.5 wt % to 4 wt %) soot resulting from operation of the engine, and wherein the lubricant composition comprises:
  • the internal combustion may have an open or closed crankcase, typically an open crankcase.
  • open crankcase ventilation are known in the art.
  • open crankcase ventilation prevents build-up of pressure in the crankcase by externally venting blow-by emission combustion products that include hydrocarbons, carbon monoxide, NOx and particulate matter.
  • closed crankcase ventilation (CCV) systems crankcase gases are typically filtered to remove oil mist and other particulates and then routed back into the intake system.
  • the internal combustion engine of the present invention may have a closed crankcase ventilation.
  • the heavy duty vehicle (HDV) containing the internal combustion engine of the present invention may have a laden mass (sometimes referred to as gross vehicle weight rating (GVWR)) of over 2700 kg (or 6000 USA pounds), or over 2900 kg, or over 3000 kg, or over 3300 kg, or over 3500 kg, or over 3700 kg, or over 3900 kg (or 8500 USA pounds).
  • a laden mass sometimes referred to as gross vehicle weight rating (GVWR)
  • GVWR gross vehicle weight rating
  • the upper limit on the laden mass or GVWR is set by national government and may be 10000 kg, or 9000 kg, or 8000 kg, or 7500 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 is for an off-highway vehicle.
  • the vehicle containing the internal combustion engine of the present invention having a laden mass of over 2700 kg (or 3,500 kg) may be a heavy duty diesel engines equipped with compression ignition engines or positive ignition natural gas (NG) or LPG engines.
  • NG positive ignition natural gas
  • LPG low-power generator
  • 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 may be a diesel engine suitable for powering a vehicle having a laden mass over 2,700 kg.
  • the centrifugal oil mist separator typically rotates at 2500 to 10000, or 4000 to 8000, or 5000 to 7000 rpm.
  • the internal combustion engine is a heavy duty diesel compression ignition (or spark assisted compression ignition) internal combustion engine.
  • the invention provides for a method of operating a centrifugal oil mist separator wherein the centrifugal oil mist separator is provided with a lubricant for separation comprising 0.1 wt % to 8 wt %, or 0.3 wt % to 6 wt % (or typically 0.5 wt % to 4 wt %) of soot, and a lubricating composition disclosed herein.
  • the present invention provides a method for lubricating an internal combustion engine as disclosed above.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704 , paragraphs [0054] to [0056] (a similar disclosure is provided in US Patent Application 2010/197536 , see [0072] to [0073]).
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • Oils of lubricating viscosity may also be defined as specified in April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils ", section 1.3 Sub-heading 1.3. "Base Stock Categories”.
  • the API Guidelines are also summarised in US Patent US 7,285,516 (see column 11, line 64 to column 12, line 10).
  • the oil of lubricating viscosity may be an API Group I to III mineral oil, a Group IV synthetic oil, or a Group V napthethnic or ester synthetic oil, or mixtures thereof. In one embodiment the oil of lubricating viscosity may be an API Group II, Group III mineral oil, or a Group IV 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.
  • the soot dispersing additive has a shear stability index of 0 to 20, or 0 to 15, or 0 to 10, or 0 to 5 as measured by dissolving an appropriate amount of the additive in a 6.0 to 6.1 mm/s 2 or cSt (measured at 100°C according to ASTM D445) Group I or Group II mineral oil to prepare a 9 - 13 mm 2 /s or cSt solution and testing the solution in the Orbahn shear test (ASTM D6278).
  • the soot dispersing additive is present at 0.2 wt % to 3 wt %, or 0.2 wt % to 2.5 wt %, or 0.3 wt % to 1.4 wt % of the lubricating composition.
  • the soot dispersing additive may have a shear stability index of 0 to 10 and be present at 0.2 wt % to 2.5 wt %, or 0.3 wt % to 1.4 wt %.
  • the soot dispersing additive may have a shear stability index of 0 to 5 and be present at 0.2 wt % to 2.5 wt %, or 0.3 wt % to 1.4 wt %.
  • the soot dispersing additives may be dispersant viscosity modifier derived from a polyolefin with a number average molecular weight of 500 to 20,000, comprising an aromatic amine moiety, or a dispersant comprising an aromatic amine moiety.
  • the lubricating composition comprises dispersant viscosity modifier comprising an aromatic amine moiety, and a dispersant comprising an aromatic amine moiety.
  • the treat rate of each may be 0.2 wt % to 3.0 wt %, or 0.3 wt % to 2.0 wt %, or 0.4 wt % to 1.5 wt % of the lubricating composition.
  • the lubricating composition of the invention contains a dispersant viscosity modifier as defined in claim 1.
  • 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 functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine.
  • an acylating agent such as maleic anhydride and an amine.
  • the dispersant viscosity modifier comprises an olefin copolymer further functionalized 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 20,000, or 6000 to 18,000, or 7000 to 15,000.
  • the olefin copolymer may have a shear stability index of 0 to 20, or 0 to 10, or 0 to 5 as measured by the Orbahn shear test (ASTM D6278) as described above.
  • the dispersant viscosity modifier 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 at least one primary or secondary amino group.
  • the reaction with an acylating agent may be conducted in the presence of a peroxide initiator and subsequently reacting the acylated olefin copolymer with an aromatic amine.
  • the dispersant viscosity modifier may be prepared in the presence of, or in the substantial absence of, an organic solvent, typically an API Group I or Group II or Group III mineral oil. API Group IV and V oils can also be used.
  • the formation of a dispersant viscosity modifier is well known in the art.
  • the dispersant viscosity modifier may include for instance those described in U.S. Patent US 7,790,661 column 2, line 48 to column 10, line 38.
  • the dispersant viscosity modifier may be prepared by grafting of an olefinic carboxylic acid acylating agent onto a polymer of 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of C 3-10 ⁇ -monoolefin, and from 0 to 15 mole percent of non-conjugated diene or triene, said polymer having an average molecular weight ranging from 5000 to 20,000, and further reacting said grafted polymer with an amine (typically an aromatic amine).
  • an amine typically an aromatic amine
  • the aromatic amine of the dispersant viscosity modifier may also include those which can be represented by the general structure NH 2 -Ar or T-NH-Ar, where T may be alkyl or aromatic, Ar is an aromatic group, including nitrogen-containing or amino-substituted aromatic groups and Ar groups including any of the following structures: as well as multiple non-condensed or linked aromatic rings.
  • Aromatic amines include those amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
  • the amines may be monoamines or polyamines.
  • the aromatic ring will typically be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
  • aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, di-(paramethylphenyl)amine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, naphthylamine, 4-(4-nitrophenylazo)aniline (disperse orange 3), sulphamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide (N-(4-aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-phenyl)-benzamide, various benzylamines such as 2,5-dimethoxybenzylamine, 4-phenylazoaniline, and substituted versions of these.
  • N-alkylanilines such as N-methylaniline and N-butylaniline
  • di-(paramethylphenyl)amine
  • 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.
  • aminocarbazoles include aminocarbazoles, benzoimidazoles, aminoindoles, aminopyrroles, amino-indazolinones, aminoperimidines, mercaptotriazoles, aminophenothiazines, aminopyridines, aminopyrazines, aminopyrimidines, pyridines, pyrazines, pyrimidines, aminothiadiazoles,
  • Suitable amines include 3-amino-N-(4-anilinophenyl)-N-isopropyl butanamide, and N-(4-anilinophenyl)-3- ⁇ (3-aminopropyl)-(cocoalkyl)amino ⁇ butanamide.
  • Other aromatic amines which can be used include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include materials of the general structure: and isomeric variations thereof, where R viii and R ix are independently alkyl or alkoxy groups such as methyl, methoxy, or ethoxy. In one instance, R viii and R ix are both - OCH 3 and the material is known as Fast Blue RR [ CAS# 6268-05-9 ].
  • R ix is -OCH 3 and R viii is -CH 3 , and the material is known as Fast Violet B [99-21-8]. When both R viii and R ix are ethoxy, the material is Fast Blue BB [120-00-3].
  • U.S. Patent 5,744,429 discloses other aromatic amine compounds, particularly aminoalkylphenothiazines. N-aromatic substituted acid amide compounds, such as those disclosed in U.S. Patent Application 2003/0030033 A1 , may also be used for the purposes of this invention. Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxyclic compound, that is, the nitrogen is not sp 2 "hybridized within an aromatic ring.
  • the aromatic amine may also comprise an amine formed by reacting an aldehyde with 4-aminodiphenylamine.
  • the resultant amine may be described as an alkylene coupled amine having at least 4 aromatic groups, at least one -NH 2 functional group, and at least 2 secondary or tertiary amino groups.
  • the aldehyde may be aliphatic, alicyclic or aromatic.
  • the aliphatic aldehyde may be linear or branched.
  • Examples of a suitable aromatic aldehyde include benzaldehyde or o-vanillin.
  • Examples of an aliphatic aldehyde include formaldehyde (or a reactive equivalent thereof such as formalin or paraformaldehyde), ethanal or propanal.
  • the aldehyde may be formaldehyde or benzaldehyde.
  • this aromatic amine may also be prepared by the methodology described in Berichte der Deutschen Chemischen Deutschen Chemischen Deutschen Chemischen
  • the aromatic amine includes 4-aminodiphenylamine, aldehyde (typically formaldehyde) coupled 4-aminodiphenylamine, 3- nitro-aniline, disperse orange-3 (4-4-nitrophenyl-azo-aniline, 4-nitrophenylazoaniline, or DOS), or mixtures thereof.
  • the soot dispersing additive may be a dispersant comprising an aromatic amine moiety obtained/obtainable by reacting a carboxylic functionalised polymer known in the art (typically a polyisobutylene succinic anhydride) with an amine having at least 4 aromatic groups (typically an aldehyde (such as formaldehyde coupled 4-aminodiphenylamine).
  • a carboxylic functionalised polymer known in the art typically a polyisobutylene succinic anhydride
  • an amine having at least 4 aromatic groups typically an aldehyde (such as formaldehyde coupled 4-aminodiphenylamine).
  • aldehyde such as formaldehyde coupled 4-aminodiphenylamine
  • the soot dispersing additive of this type is described for example in US 8,557,753 .
  • the soot dispersing additive of this type may have a shear stability index of 0 to 10, or 0 to 5 as measured by the Orbahn she
  • the resultant product of reacting the carboxylic functionalised polymer (typically a polyisobutylene succinic anhydride) with an amine having at least 4 aromatic groups may be represented by the formulae: or wherein independently each variable,R 1 may be hydrogen or a C 1-5 alkyl group (typically hydrogen); R 2 may be hydrogen or a C 1-5 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;
  • BB is a polymer backbone and may be polyisobutylene, or copolymers of polyolefins (in particular ethylene-alphaolefins such as ethylene-propylene copolymers).
  • BB may be substituted with one succinimide group as is shown in formulae above, or it may be substituted by multiple succinimide
  • additional structures may also be formed including trimers, tetramers, higher-mers or mixtures thereof.
  • 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 is other than polyisobutylene, and has maleic anhydride (or other carboxylic acid functionality) grafted thereon
  • one or more of the grafted maleic anhydride groups is a succinimide of the amine of the invention.
  • the number of succinimide groups may be 1 to 40, or 2 to 40, or 3 to 20.
  • soot dispersing additive When the soot dispersing additive is derived from 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 have, that is, 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 soot dispersing additive is derived from polyisobutylene succinic anhydride
  • the polyisobutylene succinic anhydride may be formed by reactions known in the art such as by an “ene” reaction, or a “Diels-Alder” reaction (typically obtained/obtainable by Diels Alder reaction).
  • the aromatic amine may be a reaction product of isatoic anhydride and 4-aminodiphenylamine) that can be reacted with a carboxylic functionalised polymer.
  • the carboxylic functionalised polymer may include polyisobutylene succinic anhydride, maleic anhydride-styrene copolymers, esters of maleic anhydride-styrene copolymers, (alpha-olefin maleic anhydride) copolymers; maleic anhydride-grafted styrene-ethylene-alpha olefin polymers; polymethacrylates; polyacrylates; polyhydroxycarboxylic acids (including polyhydroxystearic acid); maleic anhydride graft copolymers of (i) hydrogenated alkenyl aryl conjugated diene copolymers (in particular hydrogenated copolymers of styrene-butadiene), (ii) polyolefins grafted with maleic anhydride (
  • the aromatic amine may be a reaction product of isatoic anhydride and 4-aminodiphenylamine) that can be reacted with either polyisobutylene succinic anhydride polyolefins grafted with maleic anhydride (in particular ethylene-propylene copolymers), or mixtures thereof.
  • polyisobutylene succinic anhydride polyolefins grafted with maleic anhydride in particular ethylene-propylene copolymers
  • maleic anhydride in particular ethylene-propylene copolymers
  • the lubricating composition comprises an overbased sulfonate detergent.
  • the overbased sulfonate detergent may be present at 0.01 wt % to 0.9 wt %, or 0.05 wt % to 0.8 wt %, or 0.1 wt % to 0.7 wt %, or 0.2 wt % to 0.6 wt %.
  • the sulfonate may be prepared from a mono- or di- hydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35 or 9 to 30 carbon atoms.
  • the hydrocarbyl group may be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms.
  • a suitable alkyl group include branched and/or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl or mixtures thereof.
  • the hydrocarbyl-substituted sulfonic acid may include polypropene benzenesulfonic acid and C 16 -C 24 alkyl benzenesulfonic acid, or mixtures thereof.
  • Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500.
  • Overbased detergents are known in the art.
  • the sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919 ).
  • the predominantly linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
  • Overbased detergents are known in the art. 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.
  • metal ratio is also explained in standard textbook entitled “ Chemistry and Technology of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219 , sub-heading 7.25.
  • the overbased sulfonate of the present invention may have a metal ratio of 3.5:1 to 40:1, or 5:1 to 30:1, or 12:1 to 25:1.
  • the overbased sulfonate of the present invention has a TBN of 300 to 500 and a metal ratio of 12:1 to 25:1.
  • the overbased sulfonate detergent has a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
  • the overbased sulfonate detergent comprises an overbased calcium sulfonate, a sodium sulfonate, a magnesium sulfonate, or mixtures thereof.
  • the overbased sulfonate is/comprises a calcium sulfonate.
  • the overbased sulfonate detergent comprises a calcium sulfonate detergent having a metal ratio of 18 to 40 has a TBN of 300 to 500, or 325 to 425.
  • 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 (other than the soot dispersing additive of the present invention), detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants (other than those of the present invention), 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 invention provides a lubricating composition further comprising an overbased metal-containing detergent in addition to the overbased sulfonate detergent defined as an essential feature of the present invention.
  • the metal of the metal-containing detergent may be zinc, sodium, calcium, barium, or magnesium.
  • the metal of the metal-containing detergent may be sodium, calcium, or magnesium.
  • the overbased metal-containing detergent may be chosen from non-sulfur containing phenates, sulfur containing phenates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
  • the overbased detergent may be borated with a borating agent such as boric acid.
  • the overbased metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described; for example, in US Patents 6,429,178 ; 6,429,179 ; 6,153,565 ; and 6,281,179 .
  • phenate/salicylates e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described; for example, in US Patents 6,429,178 ; 6,429,179 ; 6,153,565 ; and 6,281,179 .
  • hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
  • an overbased metal-containing detergent may be a zinc, sodium, calcium or magnesium salt of a phenate, sulfur containing phenate, salixarate or salicylate.
  • Overbased salixarates, phenates and salicylates typically have a total base number of 180 to 450 TBN.
  • the overbased metal-containing detergent may be a calcium or magnesium an overbased detergent.
  • the lubricating composition further comprises a calcium phenate overbased detergent having a TBN of 200 to 275.
  • the lubricating composition further comprises 0.01 wt % to 2 wt %, or 0.1 to 1 wt % of a detergent different from the overbased sulfonate detergent, wherein the further detergent is chosen from non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
  • the lubricating composition further comprises a "hybrid" detergent formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, or sulfonates/phenates/salicylates.
  • a "hybrid" detergent formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, or sulfonates/phenates/salicylates.
  • the lubricating composition in a further embodiment comprises an antioxidant, wherein the antioxidant comprises a phenolic or an aminic antioxidant or mixtures thereof.
  • the antioxidants include diarylamines, alkylated diarylamines, hindered phenols, or mixtures thereof. When present the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt % of the lubricating composition.
  • the diarylamine or alkylated diarylamine may be a phenyl- ⁇ -naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof.
  • the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant may be an ester and may include, e.g., Irganox TM L-135 from Ciba.
  • suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105 .
  • the lubricating composition may in a further embodiment include a dispersant (different to the soot dispersing additive), or mixtures thereof.
  • the dispersant may be a succinimide dispersant, 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 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 chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the 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 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 , 3,467,668 , 3,501,405 , 3,542,680 , 3,576,743 , 3,632,511 , 4,234,435 , Re 26,433 , and 6,165,235 , 7,238,650 and EP Patent Application 0 355 895 A .
  • 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, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the post-treated dispersant is borated.
  • the post-treated dispersant is reacted with dimercaptothiadiazoles.
  • the post-treated dispersant is reacted with phosphoric or phosphorous acid.
  • the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in US Patent Application US2009/0054278 .
  • the dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1 to 3 wt % of the lubricating composition.
  • the lubricating composition disclosed herein further comprises an ashless dispersant comprising a succinimide dispersant different from the soot-dispersing additive of the invention, wherein the succinimide dispersant has a TBN of at least 40 mg KOH/g, and said dispersant is present at 1.2 wt % to 5 wt %, or 1.8 wt % to 4.5 wt % of the lubricating composition.
  • 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 2500.
  • the friction modifier may be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides.
  • the friction modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.
  • fatty alkyl or "fatty” in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
  • Suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products
  • Friction modifiers may also encompass materials such as sulfurised 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, sulfurised olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) 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 is at least 8.
  • the antiwear agent may in one embodiment include a citrate as is disclosed in US Patent Application 20050198894 .
  • oil-soluble titanium compounds as disclosed in US 7,727,943 and US2006/0014651 .
  • the oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
  • the oil soluble titanium compound is a titanium (IV) alkoxide.
  • the titanium alkoxide is formed from a monohydric alcohol, a polyol or mixtures thereof.
  • the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
  • the titanium alkoxide is titanium (IV) isopropoxide.
  • the titanium alkoxide is titanium (IV) 2-ethylhexoxide.
  • the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol.
  • the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic acid.
  • the oil soluble titanium compound is a titanium carboxylate.
  • the titanium (IV) carboxylate is titanium neodecanoate.
  • the lubricating composition may in one embodiment further include a phosphorus-containing antiwear agent.
  • the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof.
  • Zinc dialkyldithiophosphates are known in the art.
  • the antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricating composition.
  • EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-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 phosphit
  • 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.
  • Other viscosity modifiers may include a block copolymer comprising (i) a vinyl aromatic monomer block and (ii), a conjugated diene olefin monomer block (such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styreneisoprene copolymer), a polymethacrylate, an ethylene-alpha olefin copolymer, a hydrogenated star polymer comprising conjugated diene monomers such as butadiene or isoprene, or mixtures thereof.
  • a block copolymer comprising (i) a vinyl aromatic monomer block and (ii), a conjugated diene olefin monomer block (such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styreneisoprene copolymer), a polymethacrylate, an ethylene-alpha olefin copo
  • Pour point depressants that may be useful in the compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene copolymers, fumarate ester-vinyl acetate 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-37 TM (FN 1380) and Exxon Mineral Seal Oil TM (FN 3200).
  • the oil mist separator may be driven by an oil turbine. This, in turn, is driven by pressurized lubricant oil normally available in diesel engines. This turbine, fitted in the bottom housing of the unit, spins the centrifugal rotor. There is a separator drain that feeds the oil back to the sump.
  • the centrifugal rotor may carry a number of conical discs, stacked on top of each other, and it is here that the separation of oil mist from the blow-by gases takes place, and where soot may accumulate during engine operation. As the disc stack rotates, the dirty crankcase gas is subject to centrifugal acceleration that amounts to 25 000 m/s 2 (82 000 ft/s 2 ).
  • centrifugal forces are believed to correspond to 2 500 times the effect of the earth's gravity, make the oil droplets separate out from the gas.
  • the oil is then thrown off the edges of the discs and onto the inside wall of the oil mist separator housing, from where it runs via the drain outlet back to the sump.
  • the clean gas passes to the outlet of the unit and then on into the inlet manifold of the engine.
  • the disc stack works as a fan, extracting the blow-by gas from the crankcase and avoiding pressure drop across the unit.
  • An internal pressure control valve ensures that the crankcase pressure is always kept within a suitable working range, despite any pressure variations in the inlet manifold.
  • An oil mist separator of this type is known in the art and is sold commercially under the Alfdex ® trademark.
  • 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 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 %.
  • TBN values are (total base number) measured by the methodology described in 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 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 aluminum alloy, or an aluminum composite.
  • the vehicle powered by the compression-ignition internal combustion engine of the present invention has a maximum laden mass over 3,500 kg.
  • Soot Dispersing Molecule A Polyisobutylene-based soot dispersant (EXA).
  • 500 mL of 2M hydrochloric acid is added to a one-liter 4-neck flask equipped with an overhead stirrer, thermowell, addition funnel with nitrogen line, and condenser.
  • 184.2 g of 4-aminodiphenylamine also described as N -phenyl- p- phenylenediamine
  • the addition funnel is then charged with 40.5 g of a 37% formaldehyde solution and the solution is added drop-wise to the flask over a period of 30 minutes.
  • the flask is maintained at 100°C for 4 hours.
  • the flask is then cooled to ambient temperature. 80 g of a 50/50 wt/wt solution of sodium hydroxide in water is added over 30 minutes. At the end of the reaction, a solid product is obtained via filtration. This material may be described as a hydrocarbyl-coupled polyaromatic amine.
  • a three-liter, 4-neck flask equipped with an overhead stirrer, thermowell, subsurface inlet with nitrogen line, and Dean-Stark trap with condenser is charged with polyisobutylene succinic anhydride (1270.0 g) (where the polyisobutylene has a number average molecular weight of 2000) and diluent oil (1400.1 g).
  • the flask is heated to 90°C.
  • the hydrocarbyl-coupled polyaromatic amine described above (442.0 g) is added slowly. The temperature is then raised to 110°C and held until any residual water is removed. The temperature is then raised to 160 °C and held for 10 hours.
  • the resultant product is a dark oil with a nitrogen content of 0.65 wt %
  • a series of 15W-40 diesel lubricating compositions are prepared according to Table 1 below.
  • the compositions comprise a cross-section of soot-dispersing molecules to evaluate the tendency to plug the centrifugal oil mist separator.
  • Table 1 - Diesel Lubricant Compositions 1 EX1 EX2 EX3 EX4 CEX5 7 Group II Base Oil Balance to 100% Low Mn D-OCP 2 1.00 0.13 0.1 0.1 0 High Mn D-OCP 3 0 0 0 0 0.85 EXA - PIB-based soot dispersant 4 0 0 1.5 1.5 0 Succinimide dispersant 5 4.28 4.10 2.13 2.17 4.4 8 Overbased Ca sulfonate 0.90 0.90 1.12 0.74 0.7 9 Overbased Mg sulfonate 0 0 0 0.31 0.3 9 Overbased Ca sulfur-coupled phenate 0.81 0.81 0.63 0.68 N/A Mg sulfur-free phenate 0 0 0 0.4
  • the lubricating compositions are evaluated for oil mist separator fouling and soot handling.
  • Oil mist separator compatibility was evaluated in diesel trucks equipped with 2010EC DD15 engines manufactured by Detroit Diesel Corporation (DDC). The engines were equipped with Alfdex ® centrifugal oil mist separators. The oils were evaluated in field trials ranging from 250,000 miles to nearly 600,000 miles. All of the oil mist separator (OMS) units were inspected after the field trials were completed and rated for sludge deposit formation and drain hole plugging.
  • OMS oil mist separator
  • OMS sludge deposit rating is assigned as follows: Rating Number Description Impact 0 No sludge No problem 1 Beginning of sludge deposits Reliability not endangered 2 Light sludge Reliability not endangered 3 Severe sludge, no drain holes plugged Reliability not endangered 4 2 of 4 drain holes plugged Separator efficiency endangered 5 All drain holes plugged with sludge 100% oil carry over to T/C inlet
  • Soot handling ability may be measured in fired engine tests (e.g. Mack T 11 engine test) as well as in bench tests.
  • the lubricants are evaluated for Mack T-11 performance by methodology described in ASTM standard procedure D7156. Typically better results are obtained for samples having higher soot content at the point of 12 mm 2 /s (cSt) viscosity increase.
  • the passing limits require the lubricant to contain at least 3.5 weight % soot at 4 mm 2 /s increase in kinematic viscosity, to contain at least 6.0 weight % soot at 12 mm 2 /s increase in viscosity, and to contain at least 6.7 weight % soot at 15 mm 2 /s increase in viscosity all at 100°C per the test method.
  • Table 2 Oil Mist Separator Compatibility and T-11 Soot Handling EX1 EX2 EX3 EX4 CEX5 OIL MIST SEPARATOR NO. of UNITS 5 5 1 1 5 AVE.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)

Claims (11)

  1. Procédé de lubrification d'un moteur à combustion interne équipé d'un séparateur de brouillard d'huile centrifuge, dans lequel le lubrifiant contient 0,1 % en poids à 8 % en poids de suie résultant du fonctionnement du moteur, et dans lequel la composition lubrifiante comprend une huile de viscosité lubrifiante, et 0,2 % en poids à 3 % poids d'un additif dispersant de suie, dans lequel l'additif dispersant de suie comprend une chaîne polymère ayant une masse moléculaire moyenne en nombre de 500 à 20 000 et un indice de stabilité au cisaillement de 0 à 20 tel que mesuré par le test de cisaillement Orbahn (ASTM D6278) et est un dispersant comprenant un fragment amine aromatique obtenu en faisant réagir un anhydride sucinique de polyisobutylène avec une amine aromatique ayant la formule :
    Figure imgb0012
     dans laquelle :
    R1 est hydrogène ou un groupe alkyle en C1 à C5 ;
    R2 est hydrogène ou un groupe alkyle en C1 à C5 ;
    U est un groupe aliphatique, alicyclique ou aromatique, à condition que lorsque U est aliphatique, le groupe aliphatique est un groupe alkylène linéaire ou ramifié contenant 1 à 5, ou 1 à 2 atomes de carbone ; et
    w vaut 0 à 9 ou 0 à 3 ou 0 à 1.
  2. Procédé selon la revendication 1, dans lequel la composition lubrifiante est caractérisée en ce qu'elle présente (i) une teneur en soufre de 0,5 % en poids ou inférieur, (ii) une teneur en phosphore de 0,15 % en poids ou inférieur, et (iii) une teneur en cendres sulfatées de 0,5 % en poids à 1,5 % en poids ou inférieur.
  3. Procédé selon une quelconque revendication précédente, dans lequel la composition lubrifiante est caractérisée en ce qu'elle présente au moins une parmi (i) une teneur en soufre de 0,2 % en poids à 0,4 % en poids ou inférieur, (ii) une teneur en phosphore de 0,08 % en poids à 0,15 % en poids, et (iii) une teneur en cendres sulfatées de 0,5 % en poids à 1,5 % en poids ou inférieur.
  4. Procédé selon une quelconque revendication précédente, dans lequel la composition lubrifiante est caractérisée en ce qu'elle présente une teneur en cendres sulfatées de 0,5 % en poids à 1,2 % en poids.
  5. Procédé selon une quelconque revendication précédente, dans lequel la composition lubrifiante est caractérisée en ce qu'elle présente une teneur en indice de basicité totale (TBN) d'au moins 5 mg KOH/g, ou
    dans lequel la composition lubrifiante est caractérisée en ce qu'elle présente une teneur totale en indice de basicité totale (TBN) de 6 à 13 mg KOH/g, ou 7 à 12 mg KOH/g.
  6. Procédé selon une quelconque revendication précédente, dans lequel le véhicule alimenté par un moteur à combustion interne à allumage par compression a une masse de charge maximale supérieure à 3500 kg.
  7. Procédé selon une quelconque revendication précédente, dans lequel l'additif dispersant de suie a un indice de stabilité au cisaillement de 0 à 15, ou 0 à 10, ou 0 à 5 tel que mesuré par le test de cisaillement d'Orbahn (ASTM D6278).
  8. Procédé selon une quelconque revendication précédente, dans lequel l'additif de dispersion de suie est présent à 0,2 % en poids à 2,5 % en poids, ou 0,3 % en poids à 1,4 % en poids de la composition lubrifiante.
  9. Procédé selon une quelconque revendication précédente, dans lequel la composition lubrifiante comprend en outre un dispersant succinimide sans cendres différent de l'additif dispersant de suie, le dispersant succinimide étant présent à 1 %en poids à 8 % en poids, ou 2 % en poids à 6 % en poids.
  10. Procédé selon une quelconque revendication précédente, dans lequel le séparateur de brouillard d'huile centrifuge tourne à 2500 à 10 000, ou 4000 à 8000, ou 5000 à 7000 tr/min.
  11. Procédé selon une quelconque revendication précédente, dans lequel l'indice de stabilité au cisaillement est mesuré en dissolvant une quantité appropriée de l'additif dans dans une huile minérale de groupe I ou II de 6,0 à 6,1 mm/s2 ou cSt, mesurée à 100 °C selon la norme ASTM D445, pour préparer une solution de 9 à 13 mm2 ou cSt et en testant la solution dans le test de cisaillement Orbahn (ASTM D6278).
EP15710331.8A 2014-03-12 2015-02-23 Procédé de lubrification d'un moteur à combustion interne Active EP3116980B1 (fr)

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EP3116980A1 (fr) 2017-01-18
ES2945598T3 (es) 2023-07-04
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CN106459812A (zh) 2017-02-22
CN106459812B (zh) 2020-02-18

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