EP2078745A1 - Compositions d'huile de lubrification comportant un composé de molybdène et dialkyldithiophosphate de zinc - Google Patents

Compositions d'huile de lubrification comportant un composé de molybdène et dialkyldithiophosphate de zinc Download PDF

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Publication number
EP2078745A1
EP2078745A1 EP08251912A EP08251912A EP2078745A1 EP 2078745 A1 EP2078745 A1 EP 2078745A1 EP 08251912 A EP08251912 A EP 08251912A EP 08251912 A EP08251912 A EP 08251912A EP 2078745 A1 EP2078745 A1 EP 2078745A1
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Prior art keywords
lubricating oil
molybdenum
oil composition
compound
ppm
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP08251912A
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German (de)
English (en)
Inventor
Alexander B. Boffa
Kenij Takeoka
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Chevron Japan Ltd
Chevron Oronite Co LLC
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Chevron Japan Ltd
Chevron Oronite Co LLC
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Publication of EP2078745A1 publication Critical patent/EP2078745A1/fr
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel 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

  • lubricating oil compositions comprising a base oil, an oil soluble molybdenum compound and a zinc dithiophosphate compound. Methods of making and using the lubricating oil compositions are also described.
  • Lubricating oil compositions used to lubricate internal combustion engines contain base oil of lubricating viscosity, or a mixture of such oils, and additives used to improve the performance characteristics of the oil.
  • additives are used to improve detergency, to reduce engine wear, to provide stability against heat and oxidation, to reduce oil consumption, to inhibit corrosion, to act as a dispersant, and to reduce friction loss.
  • Some additives provide multiple benefits, such as dispersant-viscosity modifiers.
  • Other additives, while improving one characteristic of the lubricating oil have an adverse effect on other characteristics. Thus, to provide lubricating oil having optimal overall performance, it is necessary to characterize and understand all the effects of the various additives available, and carefully balance the additive content of the lubricant.
  • molybdenum compounds are generally added in amounts introducing from about 350 ppm up to 2,000 ppm of molybdenum into the oil. molybdenum compounds are effective antiwear agents and may further provide fuel economy benefits, such molybdenum compounds are expensive relative to more conventional, metal-free (ashless) organic friction modifiers
  • lubricating oil compositions that provide an improved friction reduction.
  • the lubricating oil compositions comprising
  • the base oil is present in an amount greater than about 40%, 50%, 60% or about 70% by weight of the lubricating oil compositions.
  • the lubricating oil composition disclosed herein further comprises at least one additive selected from the group consisting of antioxidants, antiwear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, multi-functional additives, viscosity index improvers, pour point depressants, foam inhibitors, metal deactivators, dispersants, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-haze additives , dyes, markers, and combinations thereof.
  • at least one additive selected from the group consisting of antioxidants, antiwear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, multi-functional additives, viscosity index improvers, pour point depressants, foam inhibitors, metal deactivators, dispersants, corrosion inhibitors, lubricity improvers, thermal stability improvers, anti-haze additives , dyes, markers, and combinations thereof.
  • the methods comprise the step of mixing
  • the methods comprise the step of operating the engine with the lubricating oil composition of provided herein.
  • Figure 1 depicts a plot of friction by High Frequency Reciprocating Rig test (HFRR) versus phosphorus content of the lubricant oil compositions described herein.
  • HFRR High Frequency Reciprocating Rig test
  • a major amount of a base oil refers to the amount of the base oil is at least 40 wt.% of the lubricating oil composition. In some embodiments, "a major amount" of a base oil refers to an amount of the base oil more than 50 wt.%, more than 60 wt.%, more than 70 wt.%, more than 80 wt.%, or more than 90 wt.% of the lubricating oil composition.
  • Standard ash content refers to the amount of metal-containing additives (e.g ., calcium, magnesium, molybdenum, zinc, etc. ) in a lubricating oil and is typically measured according to ASTM D874, which is incorporated herein by reference.
  • metal-containing additives e.g ., calcium, magnesium, molybdenum, zinc, etc.
  • a composition that is "substantially free" of a compound refers to a composition which contains less than 20 wt.%, less than 10 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, less than 0.5 wt.%, less than 0.1 wt.%, or less than 0.01 wt.% of the compound, based on the total weight of the composition.
  • a composition that is "free" of a compound refers to a composition which contains from 0.001 wt.% to 0 wt.% of the compound, based on the total weight of the composition.
  • R R L +k*(R U -R L ), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
  • lubricating oil compositions comprising:
  • the phosphorus content of the composition is about 200 to 500 ppm. In other embodiments, the phosphorus content of the composition is about 250 to 400 ppm, about 300 to 400 ppm. In certain embodiments, the SAE viscosity of the composition is 5W-20.
  • the lubricating oil compositions disclosed herein generally comprise at least one oil of lubricating viscosity.
  • Any base oil known to a skilled artisan can be used as the oil of lubricating viscosity disclosed herein.
  • Some base oils suitable for preparing the lubricating oil compositions have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapters 1 and 2 (1996 ); and A. Sequeria, Jr., “Lubricant Base Oil and Wax Processing,” New York, Marcel Decker, Chapter 6, (1994 ); and D. V. Brock, Lubrication Engineering, Vol. 43, pages 184-5, (1987 ), all of which are incorporated herein by reference.
  • the amount of the base oil in the lubricating oil composition may be from about 50 to about 99.5 wt.%, based on the total weight of the lubricating oil composition. In some embodiments, the amount of the base oil in the lubricating oil composition is from about 75 to about 99 wt.%, from about 80 to about 98.5 wt.%, or from about 80 to about 98 wt.%, based on the total weight of the lubricating oil composition.
  • the amount of base oil in the lubricant oil compositions provided herein is about 45%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 75%, 80%, 85% or about 90% by total weight of the composition.
  • the base oil is or comprises any natural or synthetic lubricating base oil fraction.
  • synthetic oils include oils, such as polyalphaolefins or PAOs, prepared from the polymerization of at least one alpha-olefin, such as ethylene, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases, such as the Fisher-Tropsch process.
  • the base oil comprises less than about 10 wt.% of one or more heavy fractions, based on the total weight of the base oil.
  • a heavy fraction refers to a lube oil fraction having a viscosity of at least about 20 cSt at 100 °C.
  • the heavy fraction has a viscosity of at least about 25 cSt or at least about 30 cSt at 100 °C.
  • the amount of the one or more heavy fractions in the base oil is less than about 10 wt.%, less than about 5 wt.%, less than about 2.5 wt.%, less than about 1 wt.%, or less than about 0.1 wt.%, based on the total weight of the base oil.
  • the base oil comprises no heavy fraction.
  • the lubricating oil compositions comprise a major amount of a base oil of lubricating viscosity.
  • the base oil has a kinematic viscosity at 100 °C from about 2 centistokes (cSt) to about 20 cSt, from about 4 centistokes (cSt) to about 16 cSt, or from about 5 cSt to about 13 cSt.
  • the kinematic viscosity of the base oils or the lubricating oil compositions disclosed herein can be measured according to ASTM D 445, which is incorporated herein by reference.
  • the base oil is or comprises a base stock or blend of base stocks.
  • the base stocks are manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
  • the base stocks comprise a rerefined stock.
  • the rerefined stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use.
  • the base oil comprises one or more of the base stocks in one or more of Groups I-V as specified in the American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (i.e., API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils ), which is incorporated herein by reference.
  • the API guideline defines a base stock as a lubricant component that may be manufactured using a variety of different processes.
  • Groups I, II and III base stocks are mineral oils, each with specific ranges of the amount of saturates, sulfur content and viscosity index.
  • Group IV base stocks are polyalphaolefins (PAO).
  • Group V base stocks include all other base stocks not included in Group I, II, III, or IV.
  • Group I, II, III, IV and V base stocks are listed in Table 1 below.
  • Table 1 Group Saturates (As determined by ASTM D 2007) Sulfur (As determined by ASTM D 2270) Viscosity Index (As determined by ASTM D 4294, ASTM D 4297 or ASTM D 3120) I Less than 90% saturates. Greater than or equal to 0.03% sulfur. Greater than or equal to 80 and less than 120. II Greater than or equal to 90% saturates, Less than or equal to 0.03% sulfur. Greater than or equal to 80 and less than 120 III Greater than or equal to 90% saturates. Less than or equal to 0.03% sulfur. Greater than or equal to 120. IV Defined as polyalphaolefins (PAO) V All other base stocks not included in Groups I, II, III or IV
  • the base oil comprises one or more of the base stocks in Group I, II, III, IV, V or a combination thereof. In other embodiments, the base oil comprises one or more of the base stocks in Group II, III, IV or a combination thereof. In further embodiments, the base oil comprises one or more of the base stocks in Group II, III, IV or a combination thereof wherein the base oil has a kinematic viscosity from about 2.5 centistokes (cSt) to about 20 cSt, from about 4 cSt to about 20 cSt, or from about 5 cSt to about 16 cSt at 100 °C.
  • cSt centistokes
  • the base oil may be selected from the group consisting of natural oils of lubricating viscosity, synthetic oils of lubricating viscosity and mixtures thereof.
  • the base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
  • the base oil of lubricating viscosity includes natural oils, such as animal oils, vegetable oils, mineral oils (e.g ., liquid petroleum oils and solvent treated or acid-treated mineral oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types), oils derived from coal or shale, and combinations thereof.
  • animal oils include bone oil, lanolin, fish oil, lard oil, dolphin oil, seal oil, shark oil, tallow oil, and whale oil.
  • vegetable oils include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, oiticica oil, jojoba oil, and meadow foam oil. Such oils may be partially or fully hydrogenated.
  • the synthetic oils of lubricating viscosity include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ether, alkylated diphenyl sulfides, as well as their derivatives, analogues and homologues thereof, and the like.
  • the synthetic oils include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups can be modified by esterification, etherification, and the like.
  • the synthetic oils include the esters of dicarboxylic acids with a variety of alcohols.
  • the synthetic oils include esters made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
  • the synthetic oils include tri-alkyl phosphate ester oils, such as tri-n-butyl phosphate and tri-iso-butyl phosphate.
  • the synthetic oils of lubricating viscosity include silicon-based oils (such as the polyakyl-, polyaryl-, polyalkoxy-, polyaryloxy-siloxane oils and silicate oils).
  • the synthetic oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
  • Base oil derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base oil.
  • Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
  • the base oil comprises a poly-alpha-olefin (PAO).
  • PAO poly-alpha-olefin
  • the poly-alpha-olefins may be derived from an alpha-olefin having from about 2 to about 30, from about 4 to about 20, or from about 6 to about 16 carbon atoms.
  • suitable poly-alpha-olefins include those derived from octene, decene, mixtures thereof, and the like.
  • These poly-alpha-olefins may have a viscosity from about 2 to about 15, from about 3 to about 12, or from about 4 to about 8 centistokes at 100 °C.
  • the poly-alpha-olefins may be used together with other base oils such as mineral oils.
  • the base oil comprises a polyalkylene glycol or a polyalkylene glycol derivative, where the terminal hydroxyl groups of the polyalkylene glycol may be modified by esterification, etherification, acetylation and the like.
  • suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof.
  • Non-limiting examples of suitable polyalkylene glycol derivatives include ethers of polyalkylene glycols (e.g., methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), mono- and polycarboxylic esters of polyalkylene glycols, and combinations thereof.
  • the polyalkylene glycol or polyalkylene glycol derivative may be used together with other base oils such as poly-alpha-olefins and mineral oils.
  • the base oil comprises any of the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, and the like) with a variety of alcohols (e.g ., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, and the like).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid,
  • Non-limiting examples of these esters include 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 like.
  • the base oil comprises a hydrocarbon prepared by the Fischer-Tropsch process.
  • the Fiseher-Tropsch process prepares hydrocarbons from gases containing hydrogen and carbon monoxide using a Fischer-Tropsch catalyst. These hydrocarbons may require further processing in order to be useful as base oils.
  • the hydrocarbons may be dewaxed, hydroisomerized, and/or hydrocracked using processes known to a person of ordinary skill in the art.
  • the base oil comprises an unrefined oil, a refined oil, a rerefined oil, or a mixture thereof.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Non-limiting examples of unrefined oils include shale oils obtained directly from retorting operations, petroleum oils obtained directly from primary distillation, and ester oils obtained directly from an esterification process and used without further treatment.
  • Refined oils are similar to the unrefined oils except the former have been further treated by one or more purification processes to improve one or more properties. Many such purification processes are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like.
  • Rerefined oils are obtained by applying to refined oils processes similar to those used to obtain refined oils.
  • Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally treated by processes directed to removal of spent additives and oil breakdown products.
  • any suitable oil-soluble molybdenum compound can be employed.
  • oil-soluble molybdenum compounds include, but are not limited to dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
  • the molybdenum compounds are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.
  • the molybdenum compound may be mono-, di-, tri- or tetra-nuclear. In certain embodiments, the compound is a dinuclear or trinuclear molybdenum compound. In one embodiment, the molybdenum compound is an organo-molybdenum compound. In another embodiment, the molybdenum compound is selected from the group consisting of molybdenum dithiocarbamates (MoDTC), molybdenum dithiophosphates, molybdenum dithiophosphinates, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides and mixtures thereof.
  • MoDTC molybdenum dithiocarbamates
  • MoDTC molybdenum dithiophosphates
  • molybdenum dithiophosphinates molybdenum xanthates
  • molybdenum thioxanthates moly
  • the molybdenum compound is present as a molybdenum dithiocarbamate or a trinuclear organo-molybdenum compound.
  • the oil-soluble molybdenum compound is selected from molybdenum dithiocarbamate, molybdenum-succinimide complex and a mixture thereof.
  • the molybdenum compound may be an acidic molybdenum compound.
  • These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent.
  • Examples of such compounds include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
  • compositions herein comprise molybdenum/sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Pat. Nos. 4,263,152 ; 4,285,822 ; 4,283,295 ; 4,272,387 ; 4,265,773 ; 4,261,843 ; 4,259,195 ; 4,259,194 and 6,562,765 ; and WO 94/06897 .
  • the basic nitrogen compound used to prepare the oxymolybdenum compounds for use herein have at least one basic nitrogen and are, in certain embodiments, oil-soluble.
  • Typical examples of such compositions are succinimides, carboxylic acid amides, hydrocarbyl monoamines, hydrocarbon polyamines, Mannich bases, phosphoramides, thiophosphoramides, phosphonamides, dispersant viscosity index improvers, and mixtures thereof.
  • Any of the nitrogen-containing compositions may be after-treated with, e.g., boron, using procedures well known in the art so long as the compositions continue to contain basic nitrogen. These after-treatments are particularly applicable to succinimides and Mannich base compositions.
  • succinimide is understood in the art to include many of the amide, imide, and amidine species which may also be formed.
  • the predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound.
  • succinimides for use herein are commercial available succinimides, such as those prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbyl group contains from about 24 to about 350 carbon atoms, and an ethylene amine, said ethylene amines being characterized by ethylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.
  • the succinimides include succinimides prepared from polyisobutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene pentamine or triethylene tetramine or mixtures thereof.
  • the cooligomers of a hydrocarbyl succinic acid or anhydride and a poly secondary amine containing at least one tertiary amino nitrogen in addition to two or more secondary amino groups.
  • the cooligomers have an average molecular weight between 1,500 and 50,000.
  • the molybdenum compound for use in the compositions herein is prepared by reacting polyisobutenyl succinic anhydride and ethylene dipiperazine.
  • carboxylic acid amide compositions are also suitable starting materials for preparing the oxymolybdenum compounds used herein. Typical of such compounds are those disclosed in U.S. Pat. No. 3,405,064 , the disclosure of which is hereby incorporated by reference. These compositions can be prepared by reacting a carboxylic acid or anhydride or ester thereof, having at least 12 to about 350 aliphatic carbon atoms in the principal aliphatic chain and, if desired, having sufficient pendant aliphatic groups to render the molecule oil soluble with an amine or a hydrocarbyl polyamine, such as an ethylene amine, to give a mono or polycarboxylic acid amide.
  • the amides are prepared from (1) a carboxylic acid of the formula R'COOH, where R' is C 12-20 alkyl or a mixture of this acid with a polyisobutenyl carboxylic acid in which the polyisobutenyl group contains from 72 to 128 carbon atoms and (2) an ethylene amine, especially triethylene tetramine or tetraethylene pentamine or mixtures thereof.
  • hydrocarbyl monoamines and hydrocarbyl polyamines such as those disclosed in U.S. Pat. No. 3,574,576 , the disclosure of which is hereby incorporated by reference.
  • the hydrocarbyl group for example alkyl, or olefinic having one or two sites of unsaturation, usually contains from 9 to 350, preferably from 20 to 200 carbon atoms.
  • hydrocarbyl polyamines are those which are derived, e.g., by reacting polyisobutenyl chloride and a polyalkylene polyamine, such as an ethylene amine, e.g., ethylene diamine, diethylene triamine, tetraethylene pentamine, 2-aminoethylpiperazine, 1,3-propylene diamine, 1,2-propylenediamine, and the like.
  • a polyalkylene polyamine such as an ethylene amine, e.g., ethylene diamine, diethylene triamine, tetraethylene pentamine, 2-aminoethylpiperazine, 1,3-propylene diamine, 1,2-propylenediamine, and the like.
  • Mannich base compositions Another class of compounds useful for supplying basic nitrogen are the Mannich base compositions. These compositions are prepared from a phenol or C 9 - 200 alkylphenol, an aldehyde, such as formaldehyde or formaldehyde precursor such as paraformaldehyde, and an amine compound.
  • the amine may be a mono or polyamine and typical compositions are prepared from an alkylamine, such as methylamine or an ethylene amine, such as, diethylene triamine, or tetraethylene pentamine, and the like.
  • the phenolic material may be sulfurized and preferably is dodecylphenol or a C 80-100 alkylphenol.
  • Typical Mannich bases which can be used are disclosed in U.S. Pat. Nos. 4,157,309 and 3,649,229 ; 3,368,972 ; and 3,539,663 , the disclosures of which are hereby incorporated by reference.
  • compositions useful for preparing the oxymolybdenum complexes employed in the lubricating oil compositions provided herein are the phosphoramides and phosphonamides such as those disclosed in U.S. Pat. Nos. 3,909,430 and 3,968,157 , the disclosures of which are hereby incorporated by reference.
  • These compositions may be prepared by forming a phosphorus compound having at least one P-N bond. They can be prepared, for example, by reacting phosphorus oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a mono-functional amine.
  • Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing from 2 to 450 or more carbon atoms, such as polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, and the like, with phosphorus pentasulfide and a nitrogen-containing compound as defined above, particularly an alkylamine, alkyldiamine, alkylpolyamine, or an alkyleneamine, such as ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like.
  • an unsaturated hydrocarbon compound containing from 2 to 450 or more carbon atoms such as polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, and the like
  • molybdenum compounds useful in the compositions provided herein are organo-molybdenum compounds of the formulae Mo(ROCS 2 ) 4 and Mo(RSCS 2 ) 4
  • R is an organic group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and in one embodiment, from 2 to 12 carbon atoms and in another embodiment, alkyl of 2 to 12 carbon atoms.
  • the molybdenum compounds are dithiocarbamates of molybdenum represented by the formula:
  • R 1 , R 2 , R 3 and R 4 are each independently a straight-chain or branched-chain alkyl group or a straight-chain or branched-chain alkenyl group having four to eighteen carbons; and X 1 , X 2 , X 3 and X 4 are each independently an oxygen atom or a sulfur atom, the ratio between the number of the oxygen atom or atoms and that of the sulfur atom or atoms with respect to X 1 through X 4 being 1/3 to 3/1.
  • R 1 , R 2 , R 3 and R 4 are each alkyl.
  • the alkyl is butyl, 2-ethylhexyl, isotridecyl or stearyl.
  • the R 1 , R 2 , R 3 and R 4 groups in one molybdenum dithiocarbamate may be identical with or different from each other. Further, two or more molybdenum dithiocarbamates having different R 1 , R 2 , R 3 and R 4 groups may be used in a mixed state.
  • organo-molybdenum compounds useful in the lubricating compositions herein are trinuclear molybdenum compounds, including those of the formula Mo 3 S k L n Q z and mixtures thereof, wherein L are independently selected ligands having organic groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. In certain embodiments, at least 21 total carbon atoms are present among all the ligands' organic groups, such as at least 25, at least 30, or at least 35 carbon atoms.
  • the ligands are independently selected from the group of: -X-R, and
  • X, X 1 , X 2 , and Y are independently selected from the group of oxygen and sulfur
  • R 1 , R 2 , and R are each independently selected from hydrogen and organic groups that may be the same or different
  • the organic groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups.
  • each ligand has the same hydrocarbyl group.
  • hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character
  • exemplary substituents include the following:
  • Hydrocarbon substituents that is, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group).
  • aliphatic for example alkyl or alkenyl
  • alicyclic for example cycloalkyl or cycloalkenyl
  • Substituted hydrocarbon substituents that is, those containing non-hydrocarbon groups which do not alter the predominantly hydrocarbyl character of the substituent Those skilled in the art are aware of suitable groups (e.g ., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, and the like).
  • suitable groups e.g ., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, and the like).
  • Hetero substituents that is, substituents which, while predominantly hydrocarbon in character, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
  • the organic groups of the ligands have a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil.
  • the number of carbon atoms in each group will generally range between about 1 to about 100, from about 1 to about 30 or between about 4 to about 20.
  • the ligands include dialkyldithiophosphate, alkylxanthate, and dialkyldithiocarbamate.
  • the ligand is dialkyldithiocarbamate.
  • Organic ligands containing two or more of the above functionalities can also serve as ligands by binding to one or more of the cores. Those skilled in the art will realize that formation of the compounds provided herein requires selection of ligands having the appropriate charge to balance the core's charge.
  • ligands may be bound or interconnected by means of one or more ligands and the ligands may be multidentate. This includes the case of a multidentate ligand having multiple connections to a single core. It is believed that oxygen and/or selenium may be substituted for sulfur in the core(s).
  • Oil-soluble or dispersible trinuclear molybdenum compounds can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
  • a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O)
  • a molybdenum source such as of (NH 4 ) 2 Mo 3 S 13 .n(H 2 O)
  • a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
  • a sulfur abstracting agent such as cyanide ions, sulfite ions, or substituted phosphines.
  • a trinuclear molybdenum-sulfur halide salt such as [M']2 [Mo 3 S 7 A6], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble or dispersible trinuclear molybdenum compound.
  • the appropriate liquid/solvent may be, for example, aqueous or organic.
  • a compound's oil solubility or dispersibility may be influenced by the number of carbon atoms in the ligand's organic groups. In the compounds herein, at least 21 total carbon atoms should be present among all the ligands' organic groups. In certain embodiments, the ligand source chosen has a sufficient number of carbon atoms in its organic groups to render the compound soluble or dispersible in the lubricating composition.
  • oil-soluble or “dispersible” used herein 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 lubricating compositions provided herein contain the molybdenum compound at a concentration of at least about 10 ppm in terms of molybdenum content In certain embodiments, the molybdenum compound is at a concentration from about 10 ppm to about 10,000 ppm in terms of molybdenum content. In certain embodiments, the molybdenum compound at a concentration from about 50 to 1500 ppm, or about 250 to 1200 ppm in terms of molybdenum content. In one embodiment, the molybdenum compound is at a concentration of about 10 ppm, 50 ppm, 100 ppm, 250 ppm, 500 ppm, 750 ppm, or 1000 ppm in terms of molybdenum content.
  • the amount of molybdenum may be determined by Inductively Coupled Plasma (ICP) emission spectroscopy using the method described in ASTM D5185.
  • ICP Inductively Coupled Plasma
  • the lubricating oil compositions provided herein additionally contain a zinc dialkyldithiophosphate compound.
  • the alkyl group in the zinc dialkyldithiophosphate compound is, for example, branched or non-branched alkyl containing 3 to 30 carbon atoms. In another embodiment, the alkyl group has 3 to 8 carbon atoms.
  • alkyl groups include a straight or branched ethyl, propyl, butyl, pentyl, methylpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
  • These zinc dialkyldithiophosphate salts can be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol 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 where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most often employed. Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction.
  • oil soluble zinc dialkyldithiophosphates may be produced from dialkyldithiophosphoric acids (DDPA) of the formula:
  • the hydroxyl alkyl compounds from which the dialkyldithiophosphoric acids are derived can be represented generically by the formula ROH or R'OH, wherein R or R' is alkyl or substituted alkyl, in one embodiment, branched or non-branched alkyl containing 3 to 30 carbon atoms. In another embodiment, R or R' is a branched or non-branched alkyl containing 3 to 8 carbon atoms.
  • alkyl groups include a straight or branched ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
  • the dialkyldithiophosphoric acids are prepared from mono-, di-, tri-, tetra-, and other polyhydroxy alkyl compounds, or mixtures of two or more of the foregoing.
  • the zinc dialkyldithiophosphate is derived from a single primary alcohol.
  • the single primary alcohol is 2-ethylhexanol.
  • the zinc dialkyldithiophosphate is derived from one or more secondary alkyl alcohols.
  • the mixture of secondary alcohols is a mixture of 2-butanol and 4-methyl-2-pentanol.
  • the zinc salts can be prepare from the dihydrocarbyl dithiophosphoric acids by reacting with a zinc compound.
  • a zinc compound In some embodiments, a basic or a neutral zinc compound is used. In other embodiments, an oxide, hydroxide or carbonate of zinc is used.
  • the phosphorus pentasulfide reactant used in the dialkyldithiophosphoric acid formation step may contain certain amounts of one or more of P 2 8 3 , P 4 S 3 , P 4 S 7 , or P 4 S 9 . Compositions as such may also contain minor amounts of free sulfur. In certain embodiments, the phosphorus pentasulfide reactant is substantially free of any of P 2 S 3 , P 4 S 3 , P 4 S 7 , and P 4 S 9 . In certain embodiments, the phosphorus pentasulfide reactant is substantially free of free sulfur.
  • the phosphorus content derived from the zinc dialkyldithiophosphate compound is about 200 to 500 ppm based on the total weight of the lubricating oil composition. In certain embodiments, the phosphorus content derived from the zinc dialkyldithiophosphate compound is about 200 to 400 ppm. In one embodiment, the phosphorus content derived from the zinc dialkyldithiophosphate compound is about 200, 250, 300, 350,400,450, 500 ppm. In one embodiment, phosphorus content derived from the zinc dialkyldithiophosphate compound is about 250 ppm.
  • additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it:
  • the lubricating oil composition provided herein comprises at least a neutral or overbased metal detergent as an additive, or additive components.
  • the metal detergents in lubricationg oil compositions acts as a neutralizer of acidic products within the oil.
  • the metal detergent prevents the formation of deposits on the surface of an engine.
  • the detergent may have additional functions, for example, antioxidant properties.
  • lubricating oil compositions contain metal detergents comprising either overbased detergents or mixtures of neutral and overbased detergents. The term "overbased" is intended to define additives which contain a metal content in excess of that required by the stoichiometry of the particular metal and the particular organic acid used.
  • the excess metal exists in the form of particles of inorganic base, e.g. a hydroxide or carbonate, surrounded by a sheath of metal salt.
  • the sheath serves to maintain the particles in dispersion in a liquid oleaginous vehicle.
  • the amount of excess metal is commonly expressed as the ratio of total equivalence of excess metal to equivalence of organic acid and is typically 0.1 to 30.
  • suitable metal detergents include sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an alkyl or alkenyl multiacid, and chemical and physical mixtures thereof.
  • suitable metal detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates and combinations thereof.
  • the metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate detergents.
  • suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li or the like.
  • An exemplary metal detergent which may be employed in the lubricating oil compositions includes overbased calcium phenate.
  • the amount of the metal detergent additive can be less than 10000 ppm, less than 1000 ppm, less than 100 ppm, or less than 10 ppm, based on the total weight of the lubricating oil composition. In some embodiments, the amount of the metal detergent is from about 0.001 wt.% to about 5 wt.%, from about 0.05 wt.% to about 3 wt.%, or from about 0.1 wt.% to about 1 wt.%, based on the total weight of the lubricating oil composition.
  • Some suitable detergents have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996 ); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 4, pages 113-136 (2003 ), both of which are incorporated herein by reference.
  • the lubricating oil compositions disclosed herein can oadditionally comprise anti wear or extreme pressure agents. Wear occurs in all equipment that has moving parts in contact. Specifically, three conditions commonly lead to wear in engines: (1) surface-to-surface contact; (2) surface contact with foreign matter; and (3) erosion due to corrosive materials. Wear resulting from surface-to-surface contact is friction or adhesive wear, from contact with foreign matter is abrasive wear, and from contact with corrosive materials is corrosive wear. Fatigue wear is an additional type of wear that is common in equipment where surfaces are not only in contact but also experience repeated stresses for prolonged periods. Abrasive wear can be prevented by installing an efficient filtration mechanism to remove the offending debris. Corrosive wear can be addressed by using additives which neutralize the reactive species that would otherwise attack the metal surfaces. The control of adhesive wear requires the use of additives called antiwear and extreme-pressure (EP) agents.
  • EP extreme-pressure
  • the metal surfaces of the equipment should be effectively separated by a lubricant film.
  • Increasing load, decreasing speed, or otherwise deviating from such optimal conditions promote metal-to-metal contact.
  • This contact typically causes a temperature increase in the contact zone due to frictional heat, which in turn leads to the loss of lubricant viscosity and hence its film-forming ability.
  • antiwear additive and EP agents offer protection by a similar mechanism.
  • EP additives require higher activation temperatures and load than antiwear additives.
  • antiwear and/or EP additives function by thermal decomposition and by forming products that react with the metal surface to form a solid protective layer.
  • This solid metal film fills the surface asperities and facilitates effective film formation, thereby reducing friction and preventing welding and surface wear.
  • Most antiwear and extreme pressure agents contain sulfur, chlorine, phosphorus, boron, or combinations thereof.
  • the classes of compounds that inhibit adhesive wear include, for example, alkyl and aryl disulfides and polysulfides; dithiocarbamates; chlorinated hydrocarbons; and phosphorus compounds such as alkyl phosphites, phosphates, dithiophosphates, and alkenylphosphonates.
  • Exemplary antiwear agents that can be included in the lubricant oil compositions provided herein include metal (e.g ., Pb, Sb, and the like) salts of dithiophosphate, metal (e.g ., Pb, Sb, and the like) salts of dithiocarbamate, metal (e.g ., Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof.
  • the amount of the anti-wear agent may vary from about 0.01 wt.% to about 5 wt.%, from about 0.05 wt.% to about 3 wt.%, or from about 0.1 wt.% to about 1 wt.%, based on the total weight of the lubricating oil composition.
  • Some suitable anti-wear agents have been described in Leslie R Rudnick, "Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter 8, pages 223-258 (2003 ), which is incorporated herein by reference.
  • the sulfated ash content of the total lubricating oil composition is less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, or less than 1 wt.%, as measured according to ASTM D874.
  • the EP agents for use in the lubricant oil compositions include alkyl and aryl disulfides and polysulfides, dithiocarbamates, chlorinated hydrocarbons, dialkyl hydrogen phosphites, and salts of alkyl phosphoric acids.
  • Methods of making these EP agents are known in the art. For example, polysulfides are synthesized from olefins either by reacting with sulfur or sulfur halides, followed by dehydrohalogenation.
  • Dialkydithiocarbamates are prepared either by neutralizing dithiocarbamic acid (which can be prepared by reacting a diakylamine and carbon disulfide at low temperature) with bases, such as antimony oxided, or by its addition to activated olefins, such as alkyl acrylates.
  • bases such as antimony oxided
  • activated olefins such as alkyl acrylates.
  • the lubricating oil compositions comprise one or more EP agents.
  • use of more that one EP agent leads to synergism.
  • synergism may be observed between sulfur and chlorine-containing EP agents.
  • An exemplary lubricating oil composition provided herein includes one or more EP agents selected from: zinc dialkyldithiophosphate (primary alkyl type & secondary alkyl type), sulfurized oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane, and lead naphthenate.
  • rust Protection against rust is an important consideration in formulating lubricants. Without protection, rust ultimately causes a loss of metal, thereby lowering the integrity of the equipment, and resulting in engine mal-function. In addition, corrosion exposes fresh metal that can wear at an accelerated rate, perpetuated by the metal ions that might be released into the fluid and act as oxidation promoters.
  • the lubricating oil composition disclosed herein can optionally comprise a rust inhibitor that can inhibit the corrosion of metal surfaces.
  • a rust inhibitor that can inhibit the corrosion of metal surfaces.
  • Any rust inhibitor known by a person of ordinary skill in the art may be used in the lubricating oil composition.
  • the rust inhibitors attach themselves to metal surfaces to form an impenetrable protective film, which can be physically or chemically adsorbed to the surface. Specifically, film formation occurs when the additives interact with the metal surface via their polar ends and associate with the lubricant via their nonpolar ends.
  • Suitable rust inhibitors may include, for example, various nonionic polyoxyethylene surface active agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol monooleate.
  • various nonionic polyoxyethylene surface active agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol monooleate.
  • Suitable rust inhibitors may further include other compounds such as, for example, monocarboxylic acids (e.g ., 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid and the like), oil-soluble polycarboxylic acids (e.g ., those produced from tall oil fatty acids, oleic acid, linoleic acid and the like), alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms ( e.g ., tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, and the like); long-chain alpha,omega-dicarboxylic acids having a molecular weight in the range of 600 to 3000 daltons and combinations thereof. Further,
  • the lubricating oil composition disclosed herein can optionally comprise a demulsifier that can promote oil-water separation in lubricating oil compositions that are exposed to water or steam. Any demulsifier known by a person of ordinary skill in the art may be used in the lubricating oil composition.
  • Non-limiting examples of suitable demulsifiers include anionic surfactants (e.g ., alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g ., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylene sorbitan ester and combinations thereof.
  • anionic surfactants e.g ., alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like
  • nonionic alkoxylated alkylphenol resins e.g ., polymers of alkylene oxides (e.g ., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble
  • the demulsifiers for use herein include block copolymers of propylene oxide or ethylene oxide and initiators, such as, for example, glycerol, phenol, formaldehyde resins, soloxanes, polyamines, and polyols.
  • initiators such as, for example, glycerol, phenol, formaldehyde resins, soloxanes, polyamines, and polyols.
  • the polymers contain about 20 to about 50% ethylene oxide. These materials concentrate at the water-oil interface and create low viscosity zones, thereby promoting droplet coalescence and gravity-driven phase separation.
  • Low molecular weight materials such as, for example, alkali metal or alkaline earth metal salts of dialkylnaphthalene sulfonic acids, are also useful in certain applications.
  • the amount of the demulsifier may vary from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.
  • Some suitable demulsifiers have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996 ), which is incorporated herein by reference.
  • the lubricating oil composition disclosed herein can optionally comprise a friction modifier that can lower the friction between moving parts.
  • Any friction modifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. They are typically long-chain molecules with a polar end group and a nonpolar linear hydrocarbon chain. The polar end groups either physically adsorb onto the metal surface or chemically react with it, while the hydrocarbon chain extend into the lubricant. The chains associated with one another and the lubricant to form a strong lubricant film.
  • Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives (e.g ., alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives ( e.g ., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-alkyl substituted amides and combinations thereof
  • the friction modifier is a saturated fatty acid containing a 13 to 18 carbon chains.
  • the amount of the friction modifier may vary from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition disclosed herein can optionally comprise a pour point depressant that can lower the pour point of the lubricating oil composition.
  • a pour point depressant Any pour point depressant known by a person of ordinary skill in the art may be used in the lubricating oil composition.
  • pour point depressants possess one or more structural features selected from: (1) polymeric structure; (2) waxy and non-waxy components; (3) comb structure comprising a short backbone with long pendant groups; and (4) broad molecular weight distribution.
  • Non-limiting examples of suitable pour point depressants include polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, alkyl fumarate polymers, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphthalene, alkylated naphthalenes, styrene esters, oligomerized alkyl phenols, phthalic acid esters, ethylene-vinyl acetate copolymers and combinations thereof.
  • the pour point depressant is selected from tetra (long-chain) alkyl silicates, phenyltrstearyloxysilane, and pentaerythritol tetrastearate.
  • the pour point depressant comprises an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, polyalkyl styrene or the like.
  • the amount of the pour point depressant may vary from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition disclosed herein can optionally comprise a foam inhibitor or an anti-foam that can break up foams in oils.
  • Any foam inhibitor or anti-foam known by a person of ordinary skill in the art may be used in the lubricating oil composition.
  • suitable anti-foams include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines and combinations thereof.
  • the anti-foam comprises glycerol monostearate, polyglycol palmitate, a trialkyl monothiophosphate, an ester of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate.
  • the amount of the anti-foam may vary from about 0.01 wt.% to about 5 wt.%, from about 0.05 wt.% to about 3 wt.%, or from about 0.1 wt.% to about 1 wt.%, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition comprises at least a metal deactivator.
  • suitable metal deactivators include disalicylidene propylenediamine, triazole derivatives, thiadiazole derivatives, and mercaptobenzimidazoles.
  • the lubricating oil composition disclosed herein can optionally comprise a dispersant that can prevent sludge, varnish, and other deposits by keeping particles suspended in a colloidal state.
  • dispersants perform these functions via one or more means selected from: (1) solubilizing polar contaminants in their micelles; (2) stabilizing colloidal dispersions in order to prevent aggregation of their particles and their separation out of oil; (3) suspending such products, if they form, in the bulk lubricant; (4) modifying soot to minimize its aggregation and oil thickening; and (5) lowering surface/interfacial energy of undesirable materials to decrease their tendency to adhere to surfaces.
  • the undesirable materials are typically formed as a result of oxidative degradation of the lubricant, the reaction of chemically reactive species such as carboxylic acids with the metal surfaces in the engine, or the decomposition of thermally unstable lubricant additives such as, for example, extreme pressure agents.
  • a dispersant molecule comprises three distinct structural features: (1) a hydrocarbyl group; (2) a polar group; and (3) a connecting group or a link.
  • the hydrocarbyl group is polymeric in nature, and has a molecular weight of at or above about 2000 Daltons, in one embodiment, at or above about 3000 Daltons, in another embodiment, at or above about 5000 Daltons, and in yet another embodiment, at or above about 8000 Daltons.
  • olefins such as polyisobutylene, polypropylene, polyalphaolefins, and mixtures thereof, can be used to make suitable polymeric dispersants.
  • the polymeric dispersant is a polyisobutylene-derived dispersant.
  • the number average molecular weight of polyisobutylene in those dispersants ranges between about 500 and about 3000 Daltons, or, in some embodiments, between about 800 to about 2000 Daltons, or in further embodiments, between about 1000 to about 2000 Daltons.
  • the polar group in the dispersant is nitrogen- or oxygen-derived.
  • Nitrogen-based dispersants are typically derived from amines.
  • the amines from which the nitrogen-based dispersants are derived are often polyalkylenepolyamines, such as, for example, diethylenetriamine and trethylenetetramine.
  • Amine-derived dispersants are also called nitrogen- or amine-dispersants, while those derived from alcohol are also called oxygen or ester dispersants.
  • Oxygen-based dispersants are typically neutral while the amine-based dispersants are typically basic.
  • Non-limiting examples of suitable dispersants include alkenyl succinimides, alkenyl succinimides modified with other organic compounds, alkenyl succinimides modified by post-treatment with ethylene carbonate or boric acid, succiamides, succinate esters, succinate ester-amides, pentaerythritols, phenate-salicylates and their post-treated analogs, alkali metal or mixed alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal borates, dispersions of alkaline-earth metal borates, polyamide ashless dispersants, benzylamines, Mannich type dispersants, phosphorus-containing dispersants, and combinations thereof.
  • the amount of the dispersant may vary from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 7 wt.%, or from about 0.1 wt.% to about 4 wt.%, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition disclosed herein can further comprise an additional antioxidant that can reduce or prevent the oxidation of the base oil.
  • an additional antioxidant that can reduce or prevent the oxidation of the base oil.
  • Any antioxidant known by a person of ordinary skill in the art may be used in the lubricating oil composition.
  • anti oxidants useful in the compositions include, but are not limited to, phenol type (phenolic) oxidation inhibitors, such as 4,4' methylene bis(2,6 di tert butylphenol), 4,4' bis(2,6 di tert-butylphenol), 4,4' bis(2 methyl 6 tert butylphenol), 2,2' methylene bis(4-methyl 6 tert butylphenol), 4,4' butylidene bis(3 methyl 6 tert butylphenol), 4,4' isopropylidene bis(2,6 di tert butylphenol), 2,2' methylene bis(4-methyl 6 nonylphenol), 2,2' isobutyliden
  • Diphenylamine type oxidation inhibitors include, but are not limited to, alkylated diphenylamine, phenyl alpha naphthylamine, and alkylated alpha naphthylamine, sulfur-based antioxidants (e.g., dilauryl-3,3'-thiodipropionate, sulfurized phenolic antioxidants and the like), phosphorous-based antioxidants ( e.g ., phosphites and the like), zinc dithiophosphate, oil-soluble copper compounds and combinations thereof.
  • sulfur-based antioxidants e.g., dilauryl-3,3'-thiodipropionate, sulfurized phenolic antioxidants and the like
  • phosphorous-based antioxidants e.g ., phosphites and the like
  • zinc dithiophosphate oil-soluble copper compounds and combinations thereof.
  • Other types of oxidation inhibitors include metal dithiocarbamate (e.g., zinc dithiocarbamate), and 15 m
  • the amount of the antioxidant may vary from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.
  • Some suitable antioxidants have been described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications,” New York, Marcel Dekker, Chapter I, pages 1-28 (2003 ), which is incorporated herein by reference.
  • a single additive may act as a dispersant as well as an oxidative inhibitor.
  • Multi-functional additives are well known in the art.
  • Other suitable multi-functional additives may include, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo pohosphoro dithioate, oxymolybdenum monoglyceride, amine-molybdenum complex compound, and sulfur-containing molybdenym complex compounds.
  • the lubricating oil composition comprises at least a viscosity index improver.
  • suitable viscosity index improvers include polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
  • the lubricating oil compositions disclosed herein can be prepared by any method known to a person of ordinary skill in the art for making lubricating oils.
  • the base oil is blended or mixed with an oil-soluble molybdenum compound; a zinc dialkyldithiophosphate and optionally an additive.
  • the oil-soluble molybdenum compound; a zinc dialkyldithiophosphate are premixed followed by addition of the base oil.
  • the oil-soluble molybdenum compound and zinc dialkyldithiophosphate can be added to the base oil individually or simultaneously.
  • the oil-soluble molybdenum compound, zinc dialkyldithiophosphate and the optional additives are added to the base oil individually in one or more additions and the additions may be in any order.
  • the ester base stocks and the additives are added to the base oil simultaneously.
  • the oil-soluble molybdenum compound, zinc dialkyldithiophosphate and the optional additives are premixed and the premix is added to the base oil along with a viscosity index improver.
  • Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients.
  • the blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., planetary mixers and double planetary mixers), a homogenizer (e.g., Gaulin homogenizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art.
  • the lubricating oil compositions provided herein is suitable for use as motor oils (that is, engine oils or crankcase oils), in a gasoline or diesel engine.
  • the lubricating oil composition provided herein is used to cool hot engine parts, keep the engine free of rust and deposits, and seal the rings and valves against leakage of combustion gases.
  • the motor oil composition comprises a base oil, oil-soluble molybdenum compound and a zinc dialkyldithiophosphate.
  • the motor oil composition may further comprises one or more other additives.
  • the motor oil composition further comprises a pour point depressant, a detergent, a dispersant, an anti-wear, an antioxidant, a friction modifier, a rust inhibitor, or a combination thereof.
  • a lubricating oil composition was prepared and used for assessing boundary lubrication properties in the High Frequency Reciprocating Rig (HFRR) test (ASTM D 6079).
  • the composition contained a major amount of a base oil of lubricating viscosity and the following additives, to provide an SAE 5W-20 finished oil;
  • a lubricating oil was prepared in accordance with the formulation of Example 1 except that 250 ppm in terms of phosphorus content of a zinc dialkyldithiophosphate was added.
  • the composition contained 250 ppm phosphorus based on the total weight of the lubricating oil composition.
  • the zinc dialkyldithiophosphate is synthesized using a mixture of C4 and C6 secondary alcohols.
  • the resulting zinc dialkyldithiophosphate is a zinc bis(O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophosphate.
  • a lubricating oil was prepared in accordance with the formulation of Example 1 except that 500 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 500 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 1 except that 750 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 750 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 1 except that 1000 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 1000 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 1 except that 700 ppm interms of molybdenum content of an oxymolybdenum-succinimide complex was used in place of the molybdenum dithiocarbamate.
  • a lubricating oil was prepared in accordance with the formulation of Example 6 except that 250 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 250 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 6 except that 500 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 500 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 6 except that 750 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 750 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 6 except that 1000 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 1000 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 1 except that the amount of molybdenum dithiocarbamate was reduced to 150 ppm in terms of molybdenum content, and 550 ppm in terms of molybdenum content of the oxymolybdenum-succinimide complex was added.
  • a lubricating oil was prepared in accordance with the formulation of Example 11 except that 250 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 250 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 11 except that 500 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 500 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 11 except that 750 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 750 ppm phosphorus based on the total weight of the lubricating oil composition.
  • a lubricating oil was prepared in accordance with the formulation of Example 10 except that 1000 ppm in terms of phosphorus content of the zinc dialkyldithiophosphate was added.
  • the composition contained 1000 ppm phosphorus based on the total weight of the lubricating oil composition.
  • the High Frequency Reciprocating Rig (HFRR) test (ASTM D 6079) is designed to evaluate boundary lubrication properties.
  • HFRR High Frequency Reciprocating Rig
  • compositions of Examples 1-15 were tested using a 120°C oil reservoir temperature and were subjected to a 1000 g load. The ball was caused to rub against the disk with a 1 mm stroke at a frequency of 20 Hz for 60 min.
  • Lubricating oil compositions with molybdenum-succinimide complex had a total molybdenum content of 700 ppm.
  • Lubricating oil composition contained a mixture of 150 ppm Mo of MoDTC and of 550 ppm Mo of molybdenum-succinimide complex. The lubricating oil composition had a total molybdenum content of 700 ppm (150 ppm Mo from MoDTC and 550 ppm Mo from Mo-succinimide complex).
  • lubricant oil compositions have been described with respect to a limited number of embodiments, the specific features of one embodiment should not be attributed to other embodiments of the subject matter claimed herein. No single embodiment is representative of all aspects of the claimed subject matter.
  • the methods may include numerous steps not mentioned herein. In other embodiments, the methods do not include, or are substantially free of, steps not enumerated herein. Variations and modifications from the described embodiments exist. It is noted that the methods for producing the compositions disclosed herein are described with reference to a number of steps. These steps can be practiced in any sequence. One or more steps may be omitted or combined but still achieve substantially the same results.
  • the appended claims intend to cover all such variations and modifications as falling within the scope of the claims.
EP08251912A 2007-12-20 2008-06-02 Compositions d'huile de lubrification comportant un composé de molybdène et dialkyldithiophosphate de zinc Withdrawn EP2078745A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012025901A1 (fr) 2010-08-27 2012-03-01 Total Raffinage Marketing Lubrifiant moteur
WO2013083777A1 (fr) 2011-12-09 2013-06-13 Total Raffinage Marketing Lubrifiant moteur pour vehicules a motorisation hybride ou micro-hybride
WO2013164457A1 (fr) 2012-05-04 2013-11-07 Total Marketing Services Composition lubrifiante pour moteur
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EP2550346A4 (fr) * 2010-03-25 2016-01-20 Vanderbilt Chemicals Llc Compositions lubrifiantes à ultrabasse teneur en phosphore
US10752858B2 (en) 2012-11-16 2020-08-25 Total Marketing Services Lubricant composition

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5796869B2 (ja) * 2011-09-29 2015-10-21 シェブロンジャパン株式会社 潤滑油組成物
JP5823329B2 (ja) * 2012-03-26 2015-11-25 Ｊｘ日鉱日石エネルギー株式会社 内燃機関用潤滑油組成物
US8400030B1 (en) * 2012-06-11 2013-03-19 Afton Chemical Corporation Hybrid electric transmission fluid
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CN104927974A (zh) * 2015-05-15 2015-09-23 农光功 润滑油
AU2016307777B2 (en) 2015-08-14 2018-11-08 Vanderbilt Chemicals, Llc Additive for lubricant compositions comprising a sulfur-containing and a sulfur-free organomolybdenum compound, and a triazole
FR3048433B1 (fr) * 2016-03-03 2020-03-13 Total Marketing Services Composition lubrifiante a base d'amines neutralisees et de molybdene
US10323205B2 (en) * 2016-05-05 2019-06-18 Afton Chemical Corporation Lubricant compositions for reducing timing chain stretch
JP6933010B2 (ja) * 2017-06-13 2021-09-08 東ソー株式会社 摩擦低減剤、及び潤滑油組成物
CN111607453A (zh) * 2020-05-22 2020-09-01 开封合成时代润滑科技有限公司 一种储存性能稳定的合成润滑油及其制备方法
CN115125050B (zh) * 2021-08-04 2023-06-02 苏州索迩电子技术有限公司 一种润滑调节油及其应用

Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3368972A (en) 1965-01-06 1968-02-13 Mobil Oil Corp High molecular weight mannich bases as engine oil additives
US3405064A (en) 1963-06-06 1968-10-08 Lubrizol Corp Lubricating oil composition
US3539663A (en) 1967-11-06 1970-11-10 Allied Chem Fibrillated fibers of a polyamide and a sulfone polyester
US3574576A (en) 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3649229A (en) 1969-12-17 1972-03-14 Mobil Oil Corp Liquid hydrocarbon fuels containing high molecular weight mannich bases
US3909430A (en) 1972-08-07 1975-09-30 Chevron Res Lubricating composition
US3968157A (en) 1972-08-07 1976-07-06 Chevron Research Company Bisphosphoramides
US4157309A (en) 1977-09-30 1979-06-05 Chevron Research Company Mannich base composition
US4164473A (en) 1977-10-20 1979-08-14 Exxon Research & Engineering Co. Organo molybdenum friction reducing antiwear additives
US4176073A (en) 1978-09-18 1979-11-27 Exxon Research & Engineering Co. Molybdenum complexes of lactone oxazoline dispersants as friction reducing antiwear additives for lubricating oils
US4176074A (en) 1978-09-18 1979-11-27 Exxon Research & Engineering Co. Molybdenum complexes of ashless oxazoline dispersants as friction reducing antiwear additives for lubricating oils
US4192757A (en) 1978-04-21 1980-03-11 Exxon Research & Engineering Company Alkyl phenol solutions of organo molybdenum complexes as friction reducing antiwear additives
US4201683A (en) 1978-04-21 1980-05-06 Exxon Research & Engineering Co. Alkanol solutions of organo molybdenum complexes as friction reducing antiwear additives
US4248720A (en) 1979-05-03 1981-02-03 Exxon Research & Engineering Co. Organo molybdenum friction-reducing antiwear additives
US4259194A (en) 1979-06-28 1981-03-31 Chevron Research Company Reaction product of ammonium tetrathiomolybdate with basic nitrogen compounds and lubricants containing same
US4259195A (en) 1979-06-28 1981-03-31 Chevron Research Company Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same
US4261843A (en) 1979-06-28 1981-04-14 Chevron Research Company Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same
US4263152A (en) 1979-06-28 1981-04-21 Chevron Research Company Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same
US4265773A (en) 1979-06-28 1981-05-05 Chevron Research Company Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same
US4272387A (en) 1979-06-28 1981-06-09 Chevron Research Company Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same
US4283295A (en) 1979-06-28 1981-08-11 Chevron Research Company Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing said composition
US4285822A (en) 1979-06-28 1981-08-25 Chevron Research Company Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition
US4289635A (en) 1980-02-01 1981-09-15 The Lubrizol Corporation Process for preparing molybdenum-containing compositions useful for improved fuel economy of internal combustion engines
US4479883A (en) 1982-01-06 1984-10-30 Exxon Research & Engineering Co. Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates
WO1994006897A1 (fr) 1992-09-11 1994-03-31 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Composition de carburant pour moteurs deux-temps
US6500786B1 (en) * 2001-11-26 2002-12-31 Infineum International Ltd. Lubricating oil composition
US6562765B1 (en) 2002-07-11 2003-05-13 Chevron Oronite Company Llc Oil compositions having improved fuel economy employing synergistic organomolybdenum components and methods for their use
WO2003064568A2 (fr) * 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Huiles pour moteurs a combustion interne a faibles teneurs en cendres, en phosphore et en soufre
EP1354933A1 (fr) * 2002-04-05 2003-10-22 Infineum International Limited Composition d'huile lubrifiante compatible avec les joints d'étenchéite des moteurs à combustion interne
EP1386957A1 (fr) * 2002-08-01 2004-02-04 Chevron Oronite Company LLC Méthodes et compositions pour réduire l'usure dans les moteurs à combustion interne, à l'aide des lubrifiants ayant un contenu en phosphore réduit
EP1405898A1 (fr) * 2002-10-02 2004-04-07 Infineum International Limited Compositions d'huiles lubrifiantes
US20060223724A1 (en) * 2005-03-29 2006-10-05 Gatto Vincent J Lubricating oil composition with reduced phosphorus levels

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4315826A (en) * 1980-08-19 1982-02-16 Texaco Inc. Reaction products of carbon disulfide with thiomolybdenum derivatives of alkenylsuccinimides and lubricants containing same
US4369119A (en) * 1981-04-03 1983-01-18 Chevron Research Company Antioxidant combinations of molybdenum complexes and organic sulfur compounds for lubricating oils
US4402840A (en) * 1981-07-01 1983-09-06 Chevron Research Company Antioxidant combinations of molybdenum complexes and organic sulfur compounds for lubricating oils
US4395343A (en) * 1981-08-07 1983-07-26 Chevron Research Company Antioxidant combinations of sulfur containing molybdenum complexes and organic sulfur compounds
US4474673A (en) * 1982-06-11 1984-10-02 Standard Oil Company (Indiana) Molybdenum-containing friction modifying additive for lubricating oils
JPH07795B2 (ja) * 1987-08-19 1995-01-11 株式会社ジャパンエナジー 内燃機関用潤滑油組成物
US5672572A (en) * 1993-05-27 1997-09-30 Arai; Katsuya Lubricating oil composition
JPH07197069A (ja) * 1993-12-30 1995-08-01 Tonen Corp 潤滑油組成物
EP0718395B1 (fr) * 1994-07-05 2002-03-06 Asahi Denka Kogyo Kabushiki Kaisha Composition d'huile de moteur
US6063741A (en) * 1994-09-05 2000-05-16 Japan Energy Corporation Engine oil composition
US5744430A (en) * 1995-04-28 1998-04-28 Nippon Oil Co., Ltd. Engine oil composition
JP3719534B2 (ja) * 1995-08-23 2005-11-24 旭電化工業株式会社 潤滑油組成物
US5814587A (en) * 1996-12-13 1998-09-29 Exxon Research And Engineering Company Lubricating oil containing an additive comprising the reaction product of molybdenum dithiocarbamate and metal dihydrocarbyl dithiophosphate
US6300291B1 (en) * 1999-05-19 2001-10-09 Infineum Usa L.P. Lubricating oil composition
JP3722484B2 (ja) * 2000-06-02 2005-11-30 シェブロンテキサコジャパン株式会社 潤滑油組成物
US7026273B2 (en) * 2001-11-09 2006-04-11 Infineum International Limited Lubricating oil compositions
US7112558B2 (en) * 2002-02-08 2006-09-26 Afton Chemical Intangibles Llc Lubricant composition containing phosphorous, molybdenum, and hydroxy-substituted dithiocarbamates
US6797677B2 (en) * 2002-05-30 2004-09-28 Afton Chemical Corporation Antioxidant combination for oxidation and deposit control in lubricants containing molybdenum and alkylated phenothiazine
US20040087452A1 (en) * 2002-10-31 2004-05-06 Noles Joe R. Lubricating oil composition
US20040087451A1 (en) * 2002-10-31 2004-05-06 Roby Stephen H. Low-phosphorus lubricating oil composition for extended drain intervals
JP2004197002A (ja) * 2002-12-19 2004-07-15 Chevron Texaco Japan Ltd 潤滑油組成物
ATE538195T1 (de) * 2004-09-27 2012-01-15 Infineum Int Ltd Schmierölzusammenstzungen mit niedrigen phosphor-,schwefel- und sulfatierten asche-gehalten
JP4718159B2 (ja) * 2004-11-05 2011-07-06 株式会社Ａｄｅｋａ エンジン油組成物

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3405064A (en) 1963-06-06 1968-10-08 Lubrizol Corp Lubricating oil composition
US3368972A (en) 1965-01-06 1968-02-13 Mobil Oil Corp High molecular weight mannich bases as engine oil additives
US3574576A (en) 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3539663A (en) 1967-11-06 1970-11-10 Allied Chem Fibrillated fibers of a polyamide and a sulfone polyester
US3649229A (en) 1969-12-17 1972-03-14 Mobil Oil Corp Liquid hydrocarbon fuels containing high molecular weight mannich bases
US3909430A (en) 1972-08-07 1975-09-30 Chevron Res Lubricating composition
US3968157A (en) 1972-08-07 1976-07-06 Chevron Research Company Bisphosphoramides
US4157309A (en) 1977-09-30 1979-06-05 Chevron Research Company Mannich base composition
US4164473A (en) 1977-10-20 1979-08-14 Exxon Research & Engineering Co. Organo molybdenum friction reducing antiwear additives
US4192757A (en) 1978-04-21 1980-03-11 Exxon Research & Engineering Company Alkyl phenol solutions of organo molybdenum complexes as friction reducing antiwear additives
US4201683A (en) 1978-04-21 1980-05-06 Exxon Research & Engineering Co. Alkanol solutions of organo molybdenum complexes as friction reducing antiwear additives
US4176073A (en) 1978-09-18 1979-11-27 Exxon Research & Engineering Co. Molybdenum complexes of lactone oxazoline dispersants as friction reducing antiwear additives for lubricating oils
US4176074A (en) 1978-09-18 1979-11-27 Exxon Research & Engineering Co. Molybdenum complexes of ashless oxazoline dispersants as friction reducing antiwear additives for lubricating oils
US4248720A (en) 1979-05-03 1981-02-03 Exxon Research & Engineering Co. Organo molybdenum friction-reducing antiwear additives
US4259194A (en) 1979-06-28 1981-03-31 Chevron Research Company Reaction product of ammonium tetrathiomolybdate with basic nitrogen compounds and lubricants containing same
US4259195A (en) 1979-06-28 1981-03-31 Chevron Research Company Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same
US4261843A (en) 1979-06-28 1981-04-14 Chevron Research Company Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same
US4263152A (en) 1979-06-28 1981-04-21 Chevron Research Company Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same
US4265773A (en) 1979-06-28 1981-05-05 Chevron Research Company Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same
US4272387A (en) 1979-06-28 1981-06-09 Chevron Research Company Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same
US4283295A (en) 1979-06-28 1981-08-11 Chevron Research Company Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing said composition
US4285822A (en) 1979-06-28 1981-08-25 Chevron Research Company Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition
US4289635A (en) 1980-02-01 1981-09-15 The Lubrizol Corporation Process for preparing molybdenum-containing compositions useful for improved fuel economy of internal combustion engines
US4479883A (en) 1982-01-06 1984-10-30 Exxon Research & Engineering Co. Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates
WO1994006897A1 (fr) 1992-09-11 1994-03-31 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Composition de carburant pour moteurs deux-temps
US6500786B1 (en) * 2001-11-26 2002-12-31 Infineum International Ltd. Lubricating oil composition
WO2003064568A2 (fr) * 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Huiles pour moteurs a combustion interne a faibles teneurs en cendres, en phosphore et en soufre
EP1354933A1 (fr) * 2002-04-05 2003-10-22 Infineum International Limited Composition d'huile lubrifiante compatible avec les joints d'étenchéite des moteurs à combustion interne
US6562765B1 (en) 2002-07-11 2003-05-13 Chevron Oronite Company Llc Oil compositions having improved fuel economy employing synergistic organomolybdenum components and methods for their use
EP1386957A1 (fr) * 2002-08-01 2004-02-04 Chevron Oronite Company LLC Méthodes et compositions pour réduire l'usure dans les moteurs à combustion interne, à l'aide des lubrifiants ayant un contenu en phosphore réduit
EP1405898A1 (fr) * 2002-10-02 2004-04-07 Infineum International Limited Compositions d'huiles lubrifiantes
US20060223724A1 (en) * 2005-03-29 2006-10-05 Gatto Vincent J Lubricating oil composition with reduced phosphorus levels

Non-Patent Citations (16)

* Cited by examiner, † Cited by third party
Title
"American Petroleum Institute", December 1996
A. SEQUERIA, JR.: "Lubricant Base Oil and Wax Processing", 1994, MARCEL DECKER
D. V. BROCK, LUBRICATION ENGINEERING, vol. 43, 1987, pages 184 - 5
LESLIE R RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER, pages: 223 - 258
LESLIE R. RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER, pages: 1 - 28
LESLIE R. RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER, pages: 113 - 136
LESLIE R. RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER, pages: 137 - 170
LESLIE R. RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER, pages: 171 - 222
LESLIE R. RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER, pages: 329 - 354
MORTIER ET AL.: "Chemistry and Technology of Lubricants", 1996, SPRINGER
MORTIER ET AL.: "Chemistry and Technology of Lubricants", 1996, SPRINGER, pages: 183 - 187
MORTIER ET AL.: "Chemistry and Technology of Lubricants", 1996, SPRINGER, pages: 187 - 189
MORTIER ET AL.: "Chemistry and Technology of Lubricants", 1996, SPRINGER, pages: 190 - 193
MORTIER ET AL.: "Chemistry and Technology of Lubricants", 1996, SPRINGER, pages: 75 - 85
MORTIER ET AL.: "Chemistry and Technology of Lubricants", vol. 3, 1996, SPRINGER, pages: 86 - 90
MORTIER ET AL.: "Chemistry and Technology of Lubricants", vol. 6, 1996, SPRINGER, pages: 190 - 193

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2550346A4 (fr) * 2010-03-25 2016-01-20 Vanderbilt Chemicals Llc Compositions lubrifiantes à ultrabasse teneur en phosphore
US9546340B2 (en) 2010-03-25 2017-01-17 Vanderbilt Chemicals, Llc Ultra low phosphorus lubricant compositions
US9896638B2 (en) 2010-03-25 2018-02-20 Vanderbilt Chemicals, Llc Ultra low phosphorus lubricant compositions
WO2012025901A1 (fr) 2010-08-27 2012-03-01 Total Raffinage Marketing Lubrifiant moteur
WO2013083777A1 (fr) 2011-12-09 2013-06-13 Total Raffinage Marketing Lubrifiant moteur pour vehicules a motorisation hybride ou micro-hybride
WO2013164457A1 (fr) 2012-05-04 2013-11-07 Total Marketing Services Composition lubrifiante pour moteur
WO2013164459A1 (fr) 2012-05-04 2013-11-07 Total Marketing Services Lubrifiant moteur pour vehicules a motorisation hybride ou micro-hybride
RU2635569C2 (ru) * 2012-05-04 2017-11-14 Тотал Маркетинг Сервисез Смазочная композиция для двигателя
US10604717B2 (en) 2012-05-04 2020-03-31 Total Marketing Services Lubricant composition for an engine
US10752858B2 (en) 2012-11-16 2020-08-25 Total Marketing Services Lubricant composition

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US20100331224A1 (en) 2010-12-30
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US20120184473A1 (en) 2012-07-19
US20090163392A1 (en) 2009-06-25

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