EP1889896B1 - Composition d'huile lubrifiante contenant des additifs détergents - Google Patents

Composition d'huile lubrifiante contenant des additifs détergents Download PDF

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Publication number
EP1889896B1
EP1889896B1 EP07111837.6A EP07111837A EP1889896B1 EP 1889896 B1 EP1889896 B1 EP 1889896B1 EP 07111837 A EP07111837 A EP 07111837A EP 1889896 B1 EP1889896 B1 EP 1889896B1
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Prior art keywords
engine
lubricating oil
lubricating
oil composition
acid
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German (de)
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EP1889896A3 (fr
EP1889896A2 (fr
Inventor
James Christian c/o Infineum UK Ltd. Dodd
Jeremy Roger c/o Infineum UK Ltd. Spencer
Tushar c/o Infineum USA L.P. Bera
Jacob c/o Infineum USA L.P. Emert
Frederick Wein c/o Infineum USA L.P. Girshick
Michael Dennis c/o Infineum USA L.P. Hoey
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Infineum International Ltd
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Infineum International Ltd
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Priority claimed from US11/500,730 external-priority patent/US7781385B2/en
Priority claimed from US11/772,896 external-priority patent/US7923420B2/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
    • 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
    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a 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
    • 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
    • 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
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C10M2203/1085—Residual fractions, e.g. bright stocks 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
    • C10M2207/021—Hydroxy compounds having hydroxy groups 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
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Definitions

  • This invention concerns lubricating oil compositions.
  • this invention concerns lubricating oil compositions for diesel engines, more specifically trunk piston diesel engine lubricating oil compositions (or trunk piston engine oil ('TPEO')) and system oils for crosshead (also referred to as two-stroke or slow speed) diesel engines.
  • trunk piston diesel engine lubricating oil compositions or trunk piston engine oil ('TPEO')
  • system oils for crosshead also referred to as two-stroke or slow speed diesel engines.
  • Trunk piston diesel engines are used in marine, power generation and rail traction applications and have a rated speed of between 300 and 1000 rpm.
  • trunk piston diesel engines a single lubricant composition is used for crankcase and cylinder lubrication. All major moving parts of the engine, i.e. the main and big end bearings, camshaft and valve gear, are lubricated by a pumped circulation system.
  • the cylinder liners are lubricated partially by splash lubrication and partially by oil from the circulation system which finds its way to the cylinder wall through holes in the piston skirt via the connecting rod and gudgeon pin.
  • Crosshead diesel engines are lubricated using two separate lubricants; the engine cylinders are lubricated using a marine diesel cylinder lubricant (or 'MDCL'), and the engine crankcase is lubricated using a separate lubricant referred to as a system oil.
  • a marine diesel cylinder lubricant or 'MDCL'
  • a separate lubricant referred to as a system oil.
  • Trunk piston diesel engines use a centrifuge system to remove contaminants such as, for example, soot or water, from the lubricating oil composition. Similar centrifuge systems are used to treat the system oil of some crosshead marine diesel engines.
  • the centrifuge system relies on the use of a sealing medium that is heavier than the lubricating oil composition.
  • the sealing medium is generally water.
  • the lubricating oil composition passes through the centrifuge system, it comes into contact with the water.
  • the lubricating oil composition therefore needs to be capable of shedding the water and remaining stable in the presence of water. If the lubricating oil composition is unable to shed the water, the water builds up in the lubricating oil composition forming an emulsion, which leads to deposits building up in the centrifuge system and prevents the centrifuge system from working properly.
  • An aim of the present invention is to provide a lubricating oil composition that is capable of shedding mediums used in centrifuge systems.
  • Marine trunk piston engines operate on residual fuels which contain high concentrations of asphaltenes. These engines have integral engine oil sumps which introduce asphaltenes into the engine lubricating oil. Asphaltenes are high molecular weight compounds with multiple fused aromatic rings, and are generally insoluble in lubricating oils. As such, they 'plate out' on to the engine surfaces causing harmful deposits. Trunk piston engines perform better when they are able to solubilise the asphaltenes.
  • a further aim of the present invention is to provide a lubricating oil composition that exhibits improved asphaltene dispersancy.
  • a lubricating oil composition having a total base number of at least 15 mg KOH/g, as determined by ASTM D2896, the composition including:
  • a method of operating a trunk piston diesel engine having a centrifuge system including a sealing medium including the step of lubricating the engine with the lubricating oil composition defined above.
  • the sealing medium is preferably water.
  • a method of operating a crosshead diesel engine having a centrifuge system including a sealing medium including the step of lubricating the engine crankcase with the lubricating oil composition defined above.
  • the sealing medium is preferably water.
  • each Ar independently represents an aromatic moiety having 0 to 3 substituents selected from the group consisting of alkyl, alkoxy, alkoxyalkyl, hydroxy, hydroxyalkyl, halo and combinations thereof; each L is independently a linking moiety comprising a carbon-carbon single bond or a linking group; each Y is independently a moiety of the formula H(O(CR 1 2 ) n ) y X-, wherein X is selected from the group consisting of (CR 1' 2 ) z , O and S; R 1 and R 1' are each independently selected from H, C 1 to C 6 alkyl and aryl; z is 1 to 10; n is 0 to 10 when X is (CR 1' 2 ) z , and 2 to 10 when X is O or S; and y is 1 to 30; each a is independently 0 to 3, with the proviso that at least one Ar moiety bears at least one
  • Aromatic moieties Ar of Formula (I) can be a mononuclear carbocyclic moiety (phenyl) or a polynuclear carbocyclic moiety.
  • Polynuclear carbocyclic moieties may comprise two or more fused rings, each ring having 4 to 10 carbon atoms (e.g., naphthalene) or may be linked mononuclear aromatic moieties, such as biphenyl, or may comprise linked, fused rings (e.g., binaphthyl).
  • suitable polynuclear carbocyclic aromatic moieties include naphthalene, anthracene, phenanthrene, cyclopentenophenanthrene, benzanthracene, dibenzanthracene, chrysene, pyrene, benzpyrene and coronene and dimer, trimer and higher polymers thereof.
  • Ar can also represent a mono- or polynuclear heterocyclic moiety.
  • Heterocyclic moieties Ar include those comprising one or more rings each containing 4 to 10 atoms, including one or more hetero atoms selected from N, O and S.
  • Suitable monocyclic heterocyclic aromatic moieties include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine and purine.
  • Suitable polynuclear heterocyclic moieties Ar include, for example, quinoline, isoquinoline, carbazole, dipyridyl, cinnoline, phthalazine, quinazoline, quinoxaline and phenanthroline. Each aromatic moiety (Ar) may be independently selected such that all moieties Ar are the same or different.
  • Polycyclic carbocyclic aromatic moieties are preferred. Most preferred are compounds of Formula I wherein each Ar is naphthalene.
  • Each aromatic moiety Ar may independently be unsubstituted or substituted with 1 to 3 substituents selected from alkyl, alkoxy alkoxyalkyl, hydroxyl, hydroxyalkyl, halo, and combinations thereof.
  • each Ar is unsubstituted (except for group(s) Y and terminal groups).
  • Each linking group (L) may be the same or different, and can be a carbon to carbon single bond between the carbon atoms of adjacent moieties Ar, or a linking group.
  • Suitable linking groups include alkylene linkages, ether linkages, diacyl linkages, ether-acyl linkages, amino linkages, amido linkages, carbamido linkages, urethane linkages, and sulfur linkage.
  • Preferred linking groups are alkylene linkages such as - CH 3 CHC(CH 3 ) 2 -, or C(CH 3 ) 2 -; diacyl linkages such as -COCO- or -CO(CH 2 ) 4 CO-; and sulfur linkages, such as -S 1 - or -S x -. More preferred linking groups are alkylene linkages, most preferably -CH 2 -.
  • Ar of Formula (I) represents naphthalene, and more preferably, Ar is derived from 2-(2-naphthyloxy)-ethanol.
  • each Ar is derived from 2-(2-naphthyloxy)-ethanol, and m is 2 to 25.
  • Y of Formula (I) is the group H(O(CR 2 ) 2 ) y O-, wherein y is 1 to 6. More preferably, Ar is naphthalene, Y is HOCH 2 CH 2 O- and L is -CH 2 -.
  • a hydroxyl aromatic compound, such as naphthol can be reacted with an alkylene carbonate (e.g., ethylene carbonate) to provide a compound of the formula AR-(Y) a .
  • an alkylene carbonate e.g., ethylene carbonate
  • the hydroxyl aromatic compound and alkylene carbonate are reacted in the presence of a base catalyst, such as aqueous sodium hydroxide, and at a temperature of from about 25 to about 300°C, preferably at a temperature of from about 50 to about 200°C.
  • a base catalyst such as aqueous sodium hydroxide
  • water may be removed from the reaction mixture by azeotropic distillation or other conventional means.
  • reaction product can be collected, and cooled to solidify.
  • a hydroxyl aromatic compound such as naphthol
  • an epoxide such as ethylene oxide, propylene oxide, butylenes oxide or styrene oxide, under similar conditions to incorporate one or more oxy-alkylene groups.
  • the resulting intermediate compound Ar-(Y) a may be further reacted with a polyhalogenated (preferably dihalogenated) hydrocarbon (e.g., 1-4-dichlorobutane, 2,2-dichloropropane, etc.), or a di- or polyolefin (e.g., butadiene, isoprene, divinylbenzene, 1,4-hexadiene, 1,5-hexadiene, etc.) to yield a compound of Formula (I) having an alkylene linking groups.
  • a polyhalogenated hydrocarbon e.g., 1-4-dichlorobutane, 2,2-dichloropropane, etc.
  • a di- or polyolefin e.g., butadiene, isoprene, divinylbenzene, 1,4-hexadiene, 1,5-hexadiene, etc.
  • Reaction of moieties Ar-(Y) a and a ketone or aldehyde provides an alkylene linked compound.
  • An acyl-linked compound can be formed by reacting moieties Ar-(Y) a with a diacid or anhydride (e.g., oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, succinic anhydride, etc.).
  • Sulfide, polysulfide, sulfinyl and sulfonyl linkages may be provided by reaction of the moieties Ar-(Y) a with a suitable difunctional sulfurizing agent (e.g., sulfur monochloride, sulfur dichloride, thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), etc.).
  • a suitable difunctional sulfurizing agent e.g., sulfur monochloride, sulfur dichloride, thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), etc.
  • Compounds of Formula (I), wherein L is a direct carbon to carbon link may be formed via oxidative coupling polymerization using a mixture of aluminum chloride and cuprous chloride, as described, for example, by P. Kovacic, et al., J. Polymer Science: Polymer Chem. Ed., 21, 457 (1983 ).
  • such compounds may be formed by reacting moieties Ar-(Y) a and an alkali metal as described, for example, in " Catalytic Benzene Coupling on Caesium/Nanoporous Carbon Catalysts", M.G. Stevens, K.M. Sellers, S. Subramoney and H.C. Foley, Chemical Communications, 2679-2680 (1988 ).
  • a reaction mixture can be neutralized with acid, preferably with an excess of acid (e.g., a sulfonic acid) and reacted with an aldehyde, preferably formaldehyde, and preferably in the presence of residual acid, to provide an alkylene, preferably methylene bridged compound of Formula (I).
  • acid e.g., a sulfonic acid
  • aldehyde preferably formaldehyde
  • residual acid e.g., a sulfonic acid
  • the degree of polymerization of the compounds of Formula I range from 2 to 101 (corresponding to a value of m of from 1 to 100), preferably from 2 to 50, most preferably from 2 to 25.
  • the compounds of Formula (II) can be formed by reacting a compound of Formula (I) with an acylating agent, and are represented by the formula: wherein:
  • Preferred acylating agents are polybutenyl succinic acylating agents such as polybutenyl, or polyisobutenyl succinic anhydride (PIBSA).
  • PIBSA polyisobutenyl succinic anhydride
  • the hydrocarbyl succinic acylating agent will have a number average molecular weight ( M n ) of from 200 to 3000, more preferably from 450 to 2500.
  • Acylating agents can be prepared by conventional methods known to those skilled in the art, such as chlorine-assisted, thermal and radical grafting methods.
  • the acylating agents can be mono- or polyfunctional.
  • the acylating agents have a functionality of less than 1.3.
  • Acylating agents are used in the manufacture of dispersants, and a more detailed description of methods for forming acylating agents is described in the description of suitable dispersants, presented infra.
  • Molar amounts of the compound of Formula (I) and the acylating agent can be adjusted such that all, or only a portion, such as 25% or more, 50% or more or 75% or more of groups Y are converted to groups Y'.
  • the compound of Formula (I) has hydroxy and/or alkyl hydroxy substituents, and such compounds are reacted with an acylating group, it is possible that all or a portion of such hydroxy and/or alkylhydroxy substituents will be converted to acyloxy or acyloxy alkyl groups.
  • a salt form of compounds of Formula (II) in which Z is an acylating group, which salts result from neutralization with base (as may occur, for example, due to interaction with a metal detergent, either in an additive package or a formulated lubricant), is also considered to be within the scope of the invention.
  • Compounds of Formula (II) can be derived from the compounds of Formula (I) by reacting the compounds of Formula (I) with the acylating agent, preferably in the presence of a liquid acid catalyst, such as sulfonic acid, e.g., dodecyl benzene sulfonic acid, paratoluene sulfonic acid or polyphosphoric acid or a solid acid catalyst such as Amberlyst-15, Amberlyst-36, zeolites, mineral acid clay or tungsten polyphosphoric acid; at a temperature of from about 0 to about 300°C, preferably from about 50 to about 250°C.
  • the polybutenyl succinic acylating agents can form diesters, acid esters or lactone esters with the compound of Formula (I).
  • the lubricating oil compositions contain from about 0.005 to 15 mass %, preferably from about 0.1 to about 5 mass %, more preferably from about 0.5 to about 2 mass % of a compound of Formula (II).
  • Oil of lubricating viscosity useful in the context of the present invention may be selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof.
  • the lubricating oil may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils.
  • the viscosity of the oil ranges from about 2 centistokes to about 40 centistokes, especially from about 4 centistokes to about 20 centistokes, as measured at 100°C.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof. Also useful are synthetic oils derived from a gas to liquid process from
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • alkyl and aryl ethers of polyoxyalkylene polymers e.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linole
  • esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • the oil of lubricating viscosity may comprise a Group I, Group II or Group III, base stock or base oil blends of the aforementioned base stocks.
  • the oil of lubricating viscosity is a Group II or Group III base stock, or a mixture thereof, or a mixture of a Group I base stock and one or more a Group II and Group III.
  • a major amount of the oil of lubricating viscosity is a Group II, Group III, Group IV or Group V base stock, or a mixture thereof.
  • the base stock, or base stock blend preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%.
  • the base stock, or base stock blend has a saturate content of greater than 90%.
  • the oil or oil blend will have a sulfur content of less than 1%, preferably less than 0.6%, most preferably less than 0.4%, by weight.
  • the volatility of the oil or oil blend is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal 16%.
  • the viscosity index (VI) of the oil or oil blend is at least 85, preferably at least 100, most preferably from about 105 to 140.
  • base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 . Said publication categorizes base stocks as follows:
  • the lubricating oil composition includes at least one overbased metal detergent.
  • a detergent is an additive that reduces formation of deposits, for example, high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps"; that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
  • a detergent comprises a polar head with a long hydrophobic tail.
  • Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • a metal compound such as an oxide or hydroxide
  • an acidic gas such as carbon dioxide
  • the detergent is preferably an alkali metal or alkaline earth metal additive such as an overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salt of a surfactant selected from phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, wherein the overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilised by the oil-soluble salt of the surfactant.
  • the metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt.
  • the metal, whether the metal of the oil-soluble or oil-insoluble salt is calcium.
  • the TBN of the detergent may be low, i.e. less than 50 mg KOH/g, medium, i.e. 50-150 mg KOH/g, or high, i.e. over 150 mg KOH/g, as determined by ASTM D2896.
  • the TBN is medium or high, i.e. more than 50 TBN.
  • the TBN is at least 60, more preferably at least 100, more preferably at least 150, and up to 500, such as up to 350 mg KOH/g, as determined by ASTM D2896.
  • Surfactants for the surfactant system of the overbased detergent preferably contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
  • hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impart the desired oil-so lubility.
  • Phenols, for use in preparing the detergents may be non-sulphurized or, preferably, sulphurized.
  • phenol as used herein includes phenols containing more than one hydroxyl group (for example, alkyl catechols) or fused aromatic rings (for example, alkyl naphthols) and phenols which have been modified by chemical reaction, for example, alkylene-bridged phenols and Mannich base-condensed phenols; and saligenin-type phenols (produced by the reaction of a phenol and an aldehyde under basic conditions).
  • Preferred phenols may be derived from the formula: where R represents a hydrocarbyl group and y represents 1 to 4. Where y is greater than 1, the hydrocarbyl groups may be the same or different.
  • Sulphurized hydrocarbyl phenols may typically be represented by the formula: where x is generally from 1 to 4. In some cases, more than two phenol molecules may be linked by S x bridges.
  • hydrocarbyl groups represented by R are advantageously alkyl groups, which advantageously contain 5 to 100, preferably 5 to 40, especially 9 to 12, carbon atoms, the average number of carbon atoms in all of the R groups being at least 9 in order to ensure adequate solubility in oil.
  • Preferred alkyl groups are nonyl (tripropylene) groups.
  • hydrocarbyl-substituted phenols will for convenience be referred to as alkyl phenols.
  • a sulphurizing agent for use in preparing a sulphurized phenol or phenate may be any compound or element which introduces -(S) x - bridging groups between the alkyl phenol monomer groups, wherein x is generally from 1 to about 4.
  • the reaction may be conducted with elemental sulphur or a halide thereof, for example, sulphur dichloride or, more preferably, sulphur monochloride. If elemental sulphur is used, the sulphurization reaction may be effected by heating the alkyl phenol compound at from 50 to 250, preferably at least 100, °C.
  • the sulphurization reaction may be effected by treating the alkyl phenol at from -10 to 120, preferably at least 60, °C.
  • the reaction may be conducted in the presence of a suitable diluent.
  • the diluent advantageously comprises a substantially inert organic diluent, for example mineral oil or an alkane.
  • the reaction is conducted for a period of time sufficient to effect substantial reaction. It is generally preferred to employ from 0.1 to 5 moles of the alkyl phenol material per equivalent of sulphurizing agent.
  • a basic catalyst for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • sulphurized alkyl phenols useful in preparing overbased detergents generally comprise diluent and unreacted alkyl phenols and generally contain from 2 to 20 mass %, preferably 4 to 14 mass %, and most preferably 6 to 12 mass%, sulphur based on the mass of the sulphurized alkyl phenol.
  • phenol as used herein includes phenols that have been modified by chemical reaction with, for example, an aldehyde, and Mannich base-condensed phenols.
  • Aldehydes with which phenols may be modified include, for example, formaldehyde, propionaldehyde and butyraldehyde.
  • the preferred aldehyde is formaldehyde.
  • Aldehyde-modified phenols suitable for use are described in, for example, US-A-5 259 967 .
  • Mannich base-condensed phenols are prepared by the reaction of a phenol, an aldehyde and an amine. Examples of suitable Mannich base-condensed phenols are described in GB-A-2 121 432 .
  • the phenols may include substituents other than those mentioned above provided that such substituents do not detract significantly from the surfactant properties of the phenols.
  • substituents are methoxy groups and halogen atoms.
  • Salicylic acids used in accordance with the invention may be non-sulphurized or sulphurized, and may be chemically modified and/or contain additional substituents, for example, as discussed above for phenols. Processes similar to those described above may also be used for sulphurizing a hydrocarbyl-substituted salicylic acid, and are well known to those skilled in the art. Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol.
  • Preferred substituents in oil-soluble salicylic acids from which overbased detergents in accordance with the invention may be derived are the substituents represented by R in the above discussion of phenols.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms.
  • Sulphonic acids used in accordance with the invention are typically obtained by sulphonation of hydrocarbyl-substituted, especially alkyl-substituted, aromatic hydrocarbons, for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • alkyl-substituted aromatic hydrocarbons for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives for example, chlorobenzene, chlorotoluene or chloronaphthalene.
  • Alkylation of aromatic hydrocarbons may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 100 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, and polyolefins, for example, polymers of ethylene, propylene, and/or butene.
  • alkylaryl sulphonic acids usually contain from 7 to 100 or more carbon atoms. They preferably contain from 16 to 80, or 12 to 40, carbon atoms per alkyl-substituted aromatic moiety, depending on the source from which they are obtained.
  • hydrocarbon solvents and/or diluent oils may also be included in the reaction mixture, as well as promoters and viscosity control agents.
  • Such sulphonic acids can be sulphurized. Whether sulphurized or non-sulphurized these sulphonic acids are believed to have surfactant properties comparable to those of sulphonic acids, rather than surfactant properties comparable to those of phenols.
  • Sulphonic acids suitable for use in accordance with the invention also include alkyl sulphonic acids, such as alkenyl sulphonic acids.
  • alkyl group suitably contains 9 to 100, advantageously 12 to 80, especially 16 to 60, carbon atoms.
  • Carboxylic acids that may be used in accordance with the invention include mono- and dicarboxylic acids. Preferred monocarboxylic acids are those containing 1 to 30, especially 8 to 24, carbon atoms.
  • Examples of monocarboxylic acids are iso-octanoic acid, stearic acid, oleic acid, palmitic acid and behenic acid.
  • Iso-octanoic acid may, if desired, be used in the form of the mixture of C 8 acid isomers sold by Exxon Chemicals under the trade name "Cekanoic".
  • Other suitable acids are those with tertiary substitution at the ⁇ -carbon atom and dicarboxylic acids with more than 2 carbon atoms separating the carboxylic groups.
  • dicarboxylic acids with more than 35, for example, 36 to 100, carbon atoms are also suitable. Unsaturated carboxylic acids can be sulphurized. Although salicylic acids contain a carboxylic group, for the purposes of the present invention they are considered to be a separate group of surfactants, and are not considered to be carboxylic acid surfactants. (Nor, although they contain a hydroxyl group, are they considered to be phenol surfactants.)
  • naphthenic acids especially naphthenic acids containing one or more alkyl groups
  • dialkylphosphonic acids dialkylthiophosphonic acids
  • dialkyldithiophosphoric acids dialkyldithiophosphoric acids
  • high molecular weight (preferably ethoxylated) alcohols preferably ethoxylated) alcohols
  • dithiocarbamic acids thiophosphines
  • dispersants of these types are well known to those skilled in the art.
  • detergents useful in the present invention are optionally sulphurized alkaline earth metal hydrocarbyl phenates that have been modified by carboxylic acids such as stearic acid, for examples as described in EP-A- 271 262 (LZ-Adibis); and phenolates as described in EP-A- 750 659 (Chevron).
  • overbased metal compounds preferably overbased calcium detergents, that contain at least two surfactant groups, such as phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, that may be obtained by manufacture of a hybrid material in which two or more different surfactant groups are incorporated during the overbasing process.
  • surfactant groups such as phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid
  • hybrid materials are an overbased calcium salt of surfactants phenol and sulphonic acid; an overbased calcium salt of surfactants phenol and carboxylic acid; an overbased calcium salt of surfactants phenol, sulphonic acid and salicylic acid; and an overbased calcium salt of surfactants phenol and salicylic acid.
  • any suitable proportions by mass may be used, preferably the mass to mass proportion of any one overbased metal compound to any other metal overbased compound is in the range of from 5:95 to 95:5; such as from 90:10 to 10:90; more preferably from 20:80 to 80:20; especially from 70:30 to 30:70; advantageously from 60:40 to 40:60.
  • the hybrid detergent preferably includes at least 5 mass% of salicylate, more preferably at least 10 mass% of salicylate.
  • the hybrid detergent preferably includes at least 5 mass% of phenate.
  • the amount of salicylate and phenate in the hybrid detergent can be determined using techniques such as chromatography, spectroscopy and/or titration, well known to persons skilled in the art.
  • the hybrid detergent may also include other surfactants such as sulphonate, sulphurized phenate, thiophosphate, naphthenate, or oil-soluble carboxylate.
  • the hybrid detergent may include at least 5 mass% of sulphonate.
  • the surfactant groups are incorporated during the overbasing process.
  • hybrid materials include, for example, those described in WO-A- 97/46643 ; WO-A- 97/46644 ; WO-A- 97/46645 ; WO-A- 97/46646 ; and WO-A-97/46647 .
  • an “overbased calcium salt of surfactants” is meant an overbased detergent in which the metal cations of the oil-insoluble metal salt are essentially calcium cations. Small amounts of other cations may be present in the oil-insoluble metal salt, but typically at least 80, more typically at least 90, for example at least 95, mole %, of the cations in the oil-insoluble metal salt, are calcium ions. Cations other than calcium may be derived, for example, from the use in the manufacture of the overbased detergent of a surfactant salt in which the cation is a metal other than calcium.
  • the metal salt of the surfactant is also calcium.
  • the TBN of the hybrid detergent is at least 300 mg KOH/g, such as at least 330 mg KOH/g, more preferably at least 350 mg KOH/g, more preferably at least 400 mg KOH/g, most preferably in the range of from 400 to 600 mg KOH/g, such as up to 500 mg KOH/g, as determined by ASTM D2896.
  • the amount of detergent in the lubricating oil composition is at least 0.5, preferably in the range of from 5 to 50, more preferably from 8 to 50, mass % based on the total amount of the lubricating oil composition.
  • the detergents may or may not be borated, and typically the boron contributing compound, e.g. the metal borate, is considered to form part of the overbasing.
  • the detergent may include both a non-borated detergent and a borated detergent.
  • the detergents preferably have a sulphated ash content (as determined by ASTM D874) of at least 0.85%, more preferably at least 1.0% and even more preferably at least 1.2%.
  • the lubricating oil composition may include at least one dispersant.
  • a dispersant is an additive for a lubricating composition whose primary function is to improve engine cleanliness.
  • Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an O, P or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • ashless dispersants are succinimides, e.g. polyisobutene succinic anhydride; and polyamine condensation products that may be borated or unborated.
  • the dispersant is preferably present in an amount from 0.5 to 5 mass %, based on the total amount of the lubricant composition.
  • the lubricating oil composition may also include at least one anti-wear additive.
  • the anti-wear additive may be metallic or non-metallic, preferably the former.
  • Dihydrocarbyl dithiophosphate metal salts are examples of the anti-wear additives.
  • the metal in the dihydrocarbyl dithiophosphate may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.
  • Zinc salts are preferred, preferably in the range of 0.1 to 1.5, preferably 0.5 to 1.3, mass %, based upon the total mass of the lubricating oil composition. They may be prepared in accordance with known techniques by firstly forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary.
  • any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
  • the preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: [(RO) (R 1 O) P(S)S] 2 Zn where R and R 1 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R 1 groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, I-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. in R and R 1 ) in the dithiophosphoric acid will generally be 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the anti-wear additive is preferably present in an amount from 0.10 to 3.0 mass %, based on the total amount of the lubricant composition.
  • the lubricating oil composition may also include at least one anti-oxidant.
  • the anti-oxidant may be aminic or phenolic.
  • secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms.
  • anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
  • the anti-oxidant if present, is provided in the composition in an amount of up to 3 mass %, based on the total amount of the lubricant composition.
  • pour point depressants such as pour point depressants, anti-foamants, metal rust inhibitors, pour point depressants and/or demulsifiers may be provided, if necessary.
  • 'oil-soluble' or 'oil-dispersable' do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • the lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
  • additive package(s) may be prepared, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby the additives can be added simultaneously to the oil of lubricating viscosity to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
  • the additives may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in the appropriate proportions, the remainder being base oil.
  • the final formulations may typically contain about 5 to 40 mass % of the additive packages(s), the remainder being base oil.
  • M n was determined by GPC using polystyrene standard corrected with the elution volume of 2-(2-naphthyloxy) ethanol as internal standard. THF was used as eluent. ( M n of 1000 dalton). 1 H and 13 C NMR confirmed the structure. FDMS and MALDI-TOF indicates the product contains mixture of methylene-linked 2-(2-naphthyloxy) ethanol oligomer of Formula (I) containing from 2 to 24 2-(2-naphthyloxy) ethanol units (m is 1 to 23).
  • Step 3 Reaction of methylene-linked 2-(2-naphthyloxy) ethanol oligomer and an acylating agent (PIBSA)
  • the following examples use a centrifuge water shedding test which evaluates the ability of an oil to shed water from a prepared test mixture of oil and water.
  • the test uses an Alfa Laval MAB103B 2.0 centrifuge coupled to a Watson Marlow peristaltic pump. The centrifuge is sealed with 800 ml of water. A measurement is made of the amount of deposits formed in the centrifuge during the test. Pre-measured amounts of water and the test oil are mixed together and then passed through the centrifuge at a rate of 2 litres/min. The test is run for an hour and a half, allowing the mixture to pass through the centrifuge about 10 times. The centrifuge is weighed before and after the test.
  • Comparative Example 1 does not include a dispersant and therefore exhibits good water separation.
  • Comparative Example 2 includes a PIBSA-PAM dispersant and demonstrates that it causes an emulsion to form between the water and the lubricating oil composition which results in the production of a larger amount of deposits.
  • the compound of formula (II) is preferred over the use of PIBSA-PAM.

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Claims (10)

  1. Composition d'huile lubrifiante ayant un indice de basicité total d'au moins 15 mg KOH/g, tel que déterminé par la norme ASTM D2896, la composition comprenant :
    - au moins 40 % en masse d'une huile de viscosité propre à la lubrification ;
    - au moins un détergent métallique surbasé ; et
    - au moins un composé de formule (II) :
    Figure imgb0009
     dans laquelle :
    chaque Ar' est un groupe naphtalène ;
    chaque L' est indépendamment un groupement de liaison comprenant une simple liaison carbone-carbone ou un groupe de liaison ;
    chaque Y' est indépendamment un groupement de formule Z(O(CR2 2)n')y'O-, où Z est dérivé d'un agent acylant polyalkyl- ou polyalcénylsuccinique ayant une Mn de 100 à 5000, et y' vaut 1 à 6 ; R2 est choisi parmi H, un groupe alkyle en C1 à C6 et aryle ; n' vaut 2 à 10 ;
    chaque a' vaut indépendamment 0 à 3, à la condition qu'au moins un groupement Ar' porte au moins un groupe Y' dans lequel Z n'est pas H ; et
    m' vaut 1 à 100.
  2. Composition d'huile lubrifiante selon la revendication 1, dans laquelle Y' est ZOCH2CH2O-, Z est un groupe acyle et L' est un groupe CH2.
  3. Composition d'huile lubrifiante selon la revendication 2, dans laquelle Ar' est dérivé du 2-(2-naphtyloxy)-éthanol et m' vaut 2 à 25.
  4. Procédé de fonctionnement d'un moteur diesel à piston-fourreau, le procédé comprenant l'étape de lubrification du moteur avec la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 3.
  5. Procédé de réduction des dépôts dans un moteur diesel à piston-fourreau, le procédé comprenant les étapes de lubrification du moteur avec la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 3, et le fonctionnement du moteur.
  6. Procédé d'amélioration de la dispersion d'asphaltène dans un moteur diesel à piston-fourreau, le procédé comprenant l'étape de lubrification du moteur avec la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 3.
  7. Procédé de fonctionnement d'un moteur diesel à crosse, le procédé comprenant l'étape de lubrification du carter du moteur avec la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 3.
  8. Procédé de réduction des dépôts dans un moteur diesel à crosse, le procédé comprenant les étapes de lubrification du moteur avec la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 3, et le fonctionnement du moteur.
  9. Procédés selon l'une quelconque des revendications 4 à 8, dans lesquels ledit moteur a un système centrifuge comprenant un milieu d'étanchéité.
  10. Procédés selon la revendication 9, dans lesquels ledit milieu d'étanchéité est l'eau.
EP07111837.6A 2006-08-08 2007-07-05 Composition d'huile lubrifiante contenant des additifs détergents Active EP1889896B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/500,730 US7781385B2 (en) 2006-08-08 2006-08-08 Lubricating oil composition
US11/772,896 US7923420B2 (en) 2007-07-03 2007-07-03 Lubricating oil composition

Publications (3)

Publication Number Publication Date
EP1889896A2 EP1889896A2 (fr) 2008-02-20
EP1889896A3 EP1889896A3 (fr) 2008-09-10
EP1889896B1 true EP1889896B1 (fr) 2019-05-29

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JP (1) JP5429728B2 (fr)
AU (1) AU2007203663B2 (fr)
CA (1) CA2596211C (fr)
ES (1) ES2731475T3 (fr)
SG (1) SG139726A1 (fr)

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US7786057B2 (en) 2007-02-08 2010-08-31 Infineum International Limited Soot dispersants and lubricating oil compositions containing same
US20090203559A1 (en) * 2008-02-08 2009-08-13 Bera Tushar Kanti Engine Lubrication
ES2641591T3 (es) 2008-05-20 2017-11-10 Infineum International Limited Lubricación de motor marino
EP2135926A1 (fr) 2008-05-20 2009-12-23 Infineum International Limited Lubrification de moteur marin
EP2123739B1 (fr) 2008-05-20 2017-09-27 Infineum International Limited Lubrification de moteur marin
ES2428237T3 (es) * 2009-04-07 2013-11-06 Infineum International Limited Lubricación de motor marino
EP2371932B1 (fr) * 2010-04-01 2018-10-17 Infineum International Limited Composition d'huile lubrifiante
EP2607462B1 (fr) * 2011-12-20 2014-03-12 Infineum International Limited Lubrification de moteur marin
GB2498635A (en) * 2011-12-21 2013-07-24 Infineum Int Ltd A method of reducing the rate of depletion of basicity of a lubricating oil composition for use in an engine

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WO2006041810A1 (fr) * 2004-10-06 2006-04-20 The Lubrizol Corporation Compositions lubrifiantes contenant des sulfonates

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US5821202A (en) * 1997-04-29 1998-10-13 The Lubrizol Corporation Hydrocarbon stream antifoulant method using bridged alkyl phenates
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CA2509735C (fr) * 2004-06-11 2012-09-25 Infineum International Limited Additifs detergents pour compositions d'huile lubrifiante
EP1642956A1 (fr) * 2004-06-11 2006-04-05 Infineum International Limited Combinaison d'additifs détergents pour compositions lubrifiantes
US7485603B2 (en) * 2005-02-18 2009-02-03 Infineum International Limited Soot dispersants and lubricating oil compositions containing same
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US2498656A (en) * 1948-05-29 1950-02-28 Petrolite Corp Processes for breaking petroleum emulsions
US2772238A (en) * 1955-06-24 1956-11-27 California Research Corp Foam-inhibited lubricating oils
US3248361A (en) * 1959-08-10 1966-04-26 Gulf Research Development Co Hydrocarbon lubricating oil composition
US4396518A (en) * 1981-10-26 1983-08-02 Exxon Research & Engineering Co. Demulsifier composition for automatic transmission fluids
WO2006041810A1 (fr) * 2004-10-06 2006-04-20 The Lubrizol Corporation Compositions lubrifiantes contenant des sulfonates

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AU2007203663B2 (en) 2011-05-12
ES2731475T3 (es) 2019-11-15
SG139726A1 (en) 2008-02-29
AU2007203663A1 (en) 2008-02-28
EP1889896A3 (fr) 2008-09-10
CA2596211A1 (fr) 2008-02-08
CA2596211C (fr) 2014-07-08
JP5429728B2 (ja) 2014-02-26
EP1889896A2 (fr) 2008-02-20
JP2008056933A (ja) 2008-03-13

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